Antifouling composition

ABSTRACT

An antifouling thermoplastic polyurethane (TPU) composition comprises a thermoplastic polyurethane and an organometallic antifouling additive and has a surface energy of from about 18 to about 26 mJ/m 2 . An article which is resistant to adhesion of organisms comprises the antifouling thermoplastic elastomer (TPU) composition having a surface with a 3-dimensional surface topography.

FIELD OF THE INVENTION

The instant invention generally relates to an antifouling thermoplasticpolyurethane composition.

DESCRIPTION OF THE RELATED ART

Biofouling is the unwanted accumulation of organic and inorganic matteron a surface from a surrounding environment. Biofouling can be costlyand dangerous.

In a marine environment, biofouling occurs when matter and marineorganisms settle, attach, and grow on surfaces which are submerged inwater. For example, biofouling can occur on the surfaces of navelvessels, bouys, underwater cables and lines, structures (e.g. bridges,piers, and docks), and even power generating facilities. The economicimpact of marine biofouling is significant; marine biofouling increaseshydrodynamic drag of marine vessels, and places a structural burden onvessels, bouys, underwater cables and lines, structures (e.g. bridges,piers, and docks), and even power generating facilities.

In a living body, biofouling occurs when matter and bacteria settle,attach, and grow on surfaces which are inserted in the living body. Forexample, biofouling can occur on the surfaces of cosmetic implants,artificial heart valves, and synthetic joints which are inserted in ahuman body. To this end, not only is the economic impact of biofoulingcostly, biofouling can be deadly.

SUMMARY OF THE INVENTION AND ADVANTAGES

An antifouling thermoplastic polyurethane (TPU) composition comprises athermoplastic polyurethane and an organometallic antifouling additiveand has a surface energy of from about 18 to about 26 mJ/m². An articlewhich is resistant to adhesion of organisms comprises the antifoulingthermoplastic elastomer (TPU) composition has a surface with a3-dimensional surface topography.

BRIEF DESCRIPTION OF THE DRAWINGS

Other advantages of the present invention will be readily appreciated,as the same becomes better understood by reference to the followingdetailed description when considered in connection with the accompanyingdrawings wherein:

FIG. 1 is a perspective top view of the barnacle growth test results onthe test plaque of Example 3;

FIG. 2 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 4 and 5;

FIG. 3 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 6a and 6b;

FIG. 4 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 7 and 8;

FIG. 5 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 10-13;

FIG. 6 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 14 and 15;

FIG. 7 is a perspective top view of the barnacle growth test results onthe test plaques of Examples 16 and 17;

FIG. 8 is a perspective top view of the barnacle growth test results onthe surfaces of the test plaques of Examples 18 and 19;

FIG. 9 is a perspective side view of a surface topography of a surfaceof Article 18A which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 10 is a perspective side view of a surface topography of a surfaceof Article 18B which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 11 is a perspective top view of a surface topography of a surfaceof Article 18C which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 12 is a perspective top view of a surface topography of a surfaceof Article 18D which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 13 is a perspective top view of a surface topography of a surfaceof Article 18E which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 14 is a perspective top view of a surface topography of a surfaceof Article 18F which is resistant to biofouling, said article formedfrom an antifouling composition;

FIG. 15 is a perspective top view of the barnacle growth test results onthe surfaces of Articles 18A-18F, as well as a perspective view of thebarnacle growth test results on the smooth surface of Article 18G;

FIG. 16 is a perspective top view of abrasion test results on thesurface of Article 18D, as well as a comparative article;

FIG. 17 is a perspective top view of the barnacle growth test results onthe surfaces of Articles 18D and 18E; and

FIG. 18 is a perspective top view of the barnacle growth test results onthe surfaces of Articles 10-13.

DETAILED DESCRIPTION OF THE INVENTION

The instant disclosure generally relates to an antifouling thermoplasticpolyurethane (TPU) composition and articles formed from the antifoulingcomposition which are resistant to biofouling. The antifouling TPUcomposition includes a thermoplastic polyurethane (TPU). The antifoulingTPU composition may include one or more types of TPU.

The TPU typically comprises the reaction product of a polyol and anisocyanate. The TPU may comprise the reaction of one or more types ofthe polyol with one or more types of the isocyanate. The polyol can beany polyol known in the art. The polyol includes one or more OHfunctional groups, typically at least two OH functional groups. Invarious embodiments, polyol is selected from the group of polyetherpolyols, polyester polyols, polyether/ester polyols, silicone polyols,fluorinated polyols, biopolyols, polytetrahydrofuran, and combinationsthereof; however, other polyols may also be employed.

In various embodiments, a polyester polyol is reacted with theisocyanate to form a polyester-based TPU. Of course, variouscombinations of different polyols can be reacted to form thepolyester-based TPU. Suitable polyester polyols may be produced from areaction of a dicarboxylic acid and a glycol having at least one primaryhydroxyl group. Suitable dicarboxylic acids may be selected from, butare not limited to, the group of adipic acid, methyl adipic acid,succinic acid, suberic acid, sebacic acid, oxalic acid, glutaric acid,pimelic acid, azelaic acid, phthalic acid, terephthalic acid,isophthalic acid, and combinations thereof. Glycols that are suitablefor use in producing the polyester polyols may be selected from, but arenot limited to, the group of ethylene glycol, butylene glycol,hexanediol, bis(hydroxymethylcyclohexane), 1,4-butanediol, diethyleneglycol, 2,2-dimethyl propylene glycol, 1,3-propylene glycol, andcombinations thereof.

In various embodiments, a polyether polyol is reacted with theisocyanate to form a polyester-based TPU. Of course, variouscombinations of different polyols can be reacted to form thepolyester-based TPU. In other words, the TPU of this embodiment is apolyether-based TPU comprising the reaction product of a polyetherpolyol and an isocyanate. Suitable polyether polyols may be selectedfrom, but are not limited to, the group of polytetramethylene glycol,polyethylene glycol, polypropylene glycol, and combinations thereof.

In various embodiments, a polytetrahydrofuran (polyTHF) is reacted withthe isocyanate to form the TPU. PolyTHF is synthesized by thepolymerization of tetrahydrofuran. The polyTHF and one or moreadditional polyols can be reacted with the isocyanate to form the TPU.Of course, various combinations of different polyols can be reacted toform the TPU. For example, the polyTHF and a polyether polyol can bereacted to form the TPU. One or more types of the polyTHF can be reactedto form the TPU. The polyTHF is also known in the art aspoly(tetramethylene ether) glycol or poly(tetramethylene oxide) and, insome embodiments, has the following general structure:

wherein n is an integer of from about 1 to about 100, alternatively fromabout 5 to about 75, alternatively from about 5 to about 50,alternatively from about 5 to about 20. Alternatively, in suchembodiments, the polyTHF can have a weight average molecular weight offrom about 225 to about 3000, alternatively from about 225 to about 275,alternatively from about 625 to about 675, alternatively from about 950to about 1050, alternatively from about 1750 to about 1850,alternatively from about 1950 to about 2050, alternatively from about2800 to about 3000, g/mol. In these embodiments, the polyol can have ahydroxyl number of from about 30 to about 1000, alternatively from about498 to about 537.4, alternatively from about 408 to about 498.7,alternatively from about 166.2 to about 179.5, alternatively from about106.9 to about 118.1, alternatively from about 60.6 to about 64.1,alternatively from about 54.7 to about 57.5, alternatively from about34.7 to about 40.1, mgKOH/g. Suitable polytetrahydrofurans/polyTHFsinclude, but are not limited to, polyTHFs commercially available fromBASF Corporation of Florham Park, N.J. under the trade name polyTHF®.

In various embodiments, a silicone polyol is reacted to form a siliconeTPU. Said differently, the silicone polyol, and the isocyanate can bechemically reacted to form the TPU. Of course, various combinations ofdifferent polyols can be reacted to form the polyester-based TPU.

As defined herein, a silicone polyol is any chemical moiety whichincludes a silicon atom and a hydroxyl group. To this end, the siliconepolyol can comprise a silicone, a polysiloxane, and/or apolyorganosiloxane. Alternatively, the silicone polyol can comprise apolyether or a polyester polyol which includes silicone. In a preferredembodiment the silicone polyol is a silicone diol and is a liquid atroom temperature.

In various embodiments, the silicone polyol comprises a silicone diolhaving the following general structure:

wherein x is an integer of from about 5 to about 15,000, alternativelyfrom about 100 to about 12,000; R is a hydrocarbon; and each respectiveR′ is a hydrocarbon or a hydrogen atom. In other words, the R′ groupscan be different as long as they are a hydrocarbon or a hydrogen atom.

In various embodiments, the silicone polyol has the following generalstructure:

wherein y is an integer of from about 5 to about 15,000, alternativelyfrom about 100 to about 12,000; R² is a hydrocarbon or a hydrogen atom.

In various preferred embodiments, the silicone polyol comprises asilicone diol having the following general structure:

wherein z is an integer of from about 5 to about 15,000, alternativelyfrom about 100 to about 12,000.

As set forth above, the silicone polyol is any chemical moiety whichincludes a silicon atom and a hydroxyl group. In some embodiments, thesilicone polyol has a hydroxyl functionality of from about 1 to about10, alternatively from about 1 to about 5, alternatively about 2.

In many embodiments, the silicone polyol is a siloxane, e.g. havingstructures such as SP1, SP2, and SP3 shown previously, which has asiloxane content of from about 0.2 to about 10, alternatively from about1 to about 5, alternatively from about 1 to about 3.5, % based on thetotal number of siloxane units. Alternatively, the silicone polyol has ahydroxyl number of from about 10 to about 1000, alternatively from about10 to about 750, alternatively from about 20 to about 200, alternativelyfrom about 15 to about 250, alternatively from about 15 to about 150,mgKOH/g.

Suitable silicone polyols include, but are not limited to, siliconepolyols commercially available from Dow Corning of Midland, Mich. underthe trade name XIAMETER®.

In various embodiments, a halogenated polyol is reacted with theisocyanate to form a halogenated TPU. Of course, various combinations ofdifferent polyols can be reacted to form the TPU. That is, thehalogenated polyol and one or more additional polyols can be reactedwith the isocyanate to form the TPU. For example, the halogenated polyoland a silicone polyol can be reacted to form the TPU. One or more typesof the halogenated polyol can be reacted to form the TPU. Thehalogenated polyol may be any suitable halogenated polyol as is known inthe art. For example, the halogenated polyol may comprise a polyesterpolyol, a polyether polyol, or combinations thereof. As another example,the halogenated polyol may comprise an aliphatic polyol, acycloaliphatic polyol, an aromatic polyol, a heterocyclic polyol, orcombination thereof.

It is to be appreciated that the term “halogenated” means comprising oneor more of a substituent comprising a halogen atom. When the halogenatedpolyol includes one or more of the substituents, the substituents mayall be the same or may be different from one another. The substituentmay be any halogen atom, such as a fluorine atom, a chlorine atom, abromine atom, an iodine atom, or an astatine atom. Typically, thehalogenated polyol comprises one or more substituents selected from thegroup of a chlorine atom, a bromine atom, and combinations thereof.Without being bound or limited by any particular theory, it is believedthat increasing the number of the substituents of the halogenated polyolallows the article to have low surface energy.

In a preferred embodiment, a fluorinated polyol is reacted with theisocyanate to form a fluorinated TPU. For example, in such anembodiment, a fluorinated diol having the following general structure isreacted to form the fluorinated TPU:

wherein p is an integer of from about 5 to about 15,000, alternativelyfrom about 100 to about 12,000; R² is a hydrocarbon or a hydrogen atom.

In various other preferred embodiments, the fluorinated polyol comprisesa silicone diol having the following general structure:

wherein q is an integer of from about 5 to about 15,000, alternativelyfrom about 100 to about 12,000.

The polyol of the subject disclosure, as is described herein, caninclude functional groups other than hydroxyl groups, such as alkenylgroups, alkoxy groups, etc. In various embodiments including suchfunctional groups, the functional groups may be terminal, pendent, orboth. Typically, the functional groups are terminal. For example, thesilicone polyol may be dimethylvinyl endblocked, divinylmethylendblocked, dimethylhydroxyl endblocked, dihydroxylmethyl endblocked,etc.

The polyol of the subject disclosure, as is described herein, can besubstituted. By “substituted,” it is meant that one or more hydrogenatoms of the polyol may be replaced with atoms other than hydrogen (e.g.a halogen atom, such as chlorine, fluorine, bromine, etc.), or a carbonatom may be replaced with an atom other than carbon, i.e., R may includeone or more heteroatoms within the chain, such as oxygen, sulfur,nitrogen, etc. For example, the silicone polyol can include fluorine. Asanother example, the polyether polyol can include bromine.

In various embodiments, a chain extender is also reacted to form theTPU. Said differently, the chain extender, the polyol, and theisocyanate can be chemically reacted to form the TPU. In one embodiment,the TPU may comprise the reaction product of the chain extender and theisocyanate in the absence of the polyol. Suitable chain extenders may beselected from, but are not limited to, the group of diols includingethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol,butenediol, butynediol, xylylene glycols, amylene glycols,1,4-phenylene-bis-beta-hydroxy ethyl ether,1,3-phenylene-bis-beta-hydroxy ethyl ether,bis-(hydroxy-methyl-cyclohexane), hexanediol, and thiodiglycol; diaminesincluding ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, cyclohexalene diamine, phenylene diamine,tolylene diamine, xylylene diamine, 3,3′-dichlorobenzidine, and3,3′-dinitrobenzidine; alkanol amines including ethanol amine,aminopropyl alcohol, 2,2-dimethyl propanol amine, 3-aminocyclohexylalcohol, and p-aminobenzyl alcohol; and combinations of any of theaforementioned chain extenders. In a preferred embodiment,1,4-butanediol is reacted with the polyol and the isocyanate to form theTPU.

As is set forth above, the TPU is the reaction product of one or moreisocyanates and one or more polyols. That is, one or more isocyanatescan be used to form the TPU. The isocyanate may be a polyisocyanatehaving two or more functional groups, e.g. two or more NCO functionalgroups. In various embodiments, the isocyanate may include, but is notlimited to, monoisocyanates, diisocyanates, polyisocyanates, biurets ofisocyanates and polyisocyanates, isocyanurates of isocyanates andpolyisocyanates, isocyanate prepolymers, and combinations thereof.Suitable isocyanates include, but are not limited to, aliphatic andaromatic isocyanates. In various embodiments, the isocyanate is selectedfrom the group of diphenylmethane diisocyanates (MDIs), polymericdiphenylmethane diisocyanates (pMDIs), toluene diisocyanates (TDIs),hexamethylene diisocyanates (HDIs), isophorone diisocyanates (IPDIs),isocyanate prepolymers, and combinations thereof.

The isocyanate may comprise an isocyanate prepolymer. The isocyanateprepolymer is typically a reaction product of an isocyanate and a polyoland/or a polyamine. The isocyanate used in the prepolymer can be anyisocyanate as described above. The polyol used to form the prepolymer istypically selected from the group of ethylene glycol, diethylene glycol,propylene glycol, dipropylene glycol, butane diol, glycerol,trimethylolpropane, triethanolamine, pentaerythritol, sorbitol,biopolyols, and combinations thereof. The polyamine used to form theprepolymer is typically selected from the group of ethylene diamine,toluene diamine, diaminodiphenylmethane and polymethylene polyphenylenepolyamines, aminoalcohols, and combinations thereof. Examples ofsuitable aminoalcohols include ethanolamine, diethanolamine,triethanolamine, and combinations thereof.

In some embodiments, the isocyanate may comprise an isocyanurated HDI,such as HDI isocyanural. Isocyanurated HDIs, which are typically highlyfunctional low-viscosity isocyanates, react with the bioresin componentto form a coating which has excellent UV, chemical, and solventresistance, has excellent adhesion and durability, and is hard yetflexible. In one such embodiment, the isocyanate has an NCO content offrom about 21.5 to about 22.5 weight percent, a viscosity at 23° C. offrom about 2,500 to about 4,500 mPa·sec, and a percent solids of about100 weight percent.

Specific isocyanates that may be used include, but are not limited to,toluene diisocyanate; 4,4′-diphenylmethane diisocyanate; m-phenylenediisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1; 3-phenyl enediisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate;1,4-dicyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate,2,4,6-toluylene triisocyanate,1,3-diisopropylphenylene-2,4-dissocyanate;1-methyl-3,5-diethylphenylene-2,4-diisocyanate;1,3,5-triethylphenylene-2,4-diisocyanate;1,3,5-triisoproply-phenylene-2,4-diisocyanate;3,3′-diethyl-bisphenyl-4,4′-diisocyanate;3,5,3′,5′-tetraethyl-diphenylmethane-4,4′-diisocyanate;3,5,3′,5′-tetraisopropyldiphenylmethane-4,4′-diisocyanate;1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate;1,3,5-triethylbenzene-2,4,6-triisocyanate; 1-ethyl-3,5-diisopropylbenzene-2,4,6-triisocyanate and 1,3,5-triisopropylbenzene-2,4,6-triisocyanate. Other suitable polyamide imide coatings canalso be prepared from aromatic diisocyanates or isocyanates having oneor two aryl, alkyl, arakyl or alkoxy substituents wherein at least oneof these substituents has at least two carbon atoms. Of course, variouscombinations of the isocyanates referenced herein can be used to formthe TPU.

Suitable isocyanates include, but are not limited to, isocyanatescommercially available from BASF Corporation of Florham Park, N.J. underthe trade names LUPRANATE® and BASONAT®.

In some embodiments, the TPU comprises the reaction product of apolyetherol, an isocyanate, and a chain extender. For example, the TPUcomprises the reaction product of polytetramethylene ether glycolobtained by the polymerization of tetrahydrofuran, a chain extender, andan aromatic isocyanate.

The polyol(s) and the isocyanate may be reacted in the presence ofvarious additives to form the TPU. The one or more additives that may bepresent while the TPU is being formed, or present in the TPU onceformed, include additives selected from the group of anti-foamingagents, processing additives, plasticizers, chain terminators,surface-active agents, adhesion promoters, flame retardants,anti-oxidants, water scavengers, fumed silicas, dyes, ultraviolet lightstabilizers, fillers, thixotropic agents, transition metals, catalysts,blowing agents, surfactants, cross-linkers, inert diluents, andcombinations thereof. The additive(s) may be included in any amount asdesired by those of skill in the art.

Typically, the isocyanate and the polyol and/or chain extender arereacted at an isocyanate index of from about 90 to about 115,alternatively from about 95 to about 105, alternatively from about 105to about 110.

In some embodiments, the antifouling TPU composition comprises thereaction product of: (A) a polyetherol; (B) a silicone polyol; (C) achain extender different than said polyetherol and said silicone polyol;and (D) an isocyanate. In some such embodiments, the polyetherolcomprises polytetramethylene ether glycol obtained by the polymerizationof tetrahydrofuran and has a hydroxyl number of from about 30 to about1000 mgKOH/g. In some such embodiments, the silicone polyol (B)comprises an OH end-blocked polydimethylsiloxane having a silanol havinga hydroxyl number of about 2, and a viscosity at 25° C. of from about 20to about 200, cSt. In some such embodiments, the chain extendercomprises 1,4-butanediol. Hydroxy functional components (A) through (D)are, in some such embodiments, reacted with diphenylmethane diisocyanate(MDI) and/or polymeric diphenylmethane diisocyanate (pMDI).

In embodiments where the antifouling TPU composition comprises thereaction product of: (A) a polyetherol; (B) a silicone polyol; (C) achain extender different than said polyetherol and said silicone polyol;and (D) an isocyanate, reactants (A) through (D) are reacted in thefollowing amounts to form the reaction product: from about 25 to about75, alternatively from about 40 to about 60, weight percent of saidpolyetherol; from about 2 to about 25, alternatively from about 2 toabout 12, weight percent of said silicone polyol; from about 1 to about15, alternatively from about 5 to about 10, weight percent of said chainextender; and from about 10 to about 60, alternatively about 25 to about45, weight percent of said isocyanate. Weight percent of reactants (A)through (D) is based on the total weight of reactants (A) through (D)which are reacted to form said reaction product.

Obviously, embodiments where the antifouling TPU composition comprisesthe reaction product of: (A) the polyetherol; (B) the silicone polyol;(C) the chain extender different than said polyetherol and the siliconepolyol; and (D) an isocyanate are not limiting in nature. Furtherembodiments utilizing the various reactants, e.g. polyols, chainextenders and isocyanates are contemplated. For example, in someembodiments, a fluorinated polyol is reacted into said reaction product.In other such embodiments, a fluorinated polyol can be used in lieu ofthe silicone polyol. Likewise, the antifouling TPU composition is notlimited to the reaction product described above. For example, theantifouling TPU composition can also include an antifouling additive,e.g. zinc pyrithione and/or other additives as is described below.

The antifouling TPU composition has a surface energy of from about 18 toabout 26 mJ/m².

An article comprising the antifouling TPU composition and having asurface with a 3-dimensional surface topography is resistant to adhesionof organisms.

The TPU can be any TPU known in the art. In one embodiment, the TPU isselected from the group of polyester-based TPUs, polyether-based TPUs,silicon TPUs, halogenated TPUs, and combinations thereof. For purposesof the subject disclosure, a “polyester-based” TPU is a TPU thatincludes at least two ester groups present therein and/or is formed froma reactant that includes a polyester bond. Likewise, also for purposesof the instant application, a “polyether-based” TPU is a TPU thatincludes at least two ether groups present therein and/or is formed froma reactant that includes a polyether bond. It is to be appreciated thatfor both polyester-based and polyether-based TPUs, reactants can be usedto form the TPUs that do not include polyester or polyether groupstherein. For purposes of the subject disclosure, a silicone TPU is a TPUthat includes a silicon atom and/or is formed from a reactant thatincludes a silicon atom. Of course, the silicon modified TPU can bepolyester-based and/or polyether-based. Further, it is also to beappreciated that suitable TPUs for purposes of this disclosure are notlimited to polyester-based, polyether-based TPUs, and silicone TPUs, andthat other TPUs may also be suitable that do not include ether or estergroups present therein.

Suitable TPUs include, but are not limited to, TPUs commerciallyavailable from BASF Corporation of Florham Park, N.J. under the tradename ELASTOLLAN®. Further, various suitable TPUs commercially availableunder the trade name ELASTOLLAN® include ELASTOLLAN® 600 Series TPUs,800 Series TPUs, 1100 Series TPUs, 1200 Series TPUs, B Series TPUs, CSeries TPUs, S Series TPUs, and Specialty TPUs.

Referring now to the TPU, in various embodiments, the TPU typically has:a Shore D Hardness of from about 40 to about 100 pts as determined byDIN53505; and a specific gravity of from about 1.1 to about 1.3,alternatively from about 1.17 to about 1.23, g/cm³; a tensile strengthof from about 2,000 to about 10,000, alternatively from about 3,000 toabout 9,000, psi at 23° C. as determined by ASTM D412; a tensile stressat 100% elongation of from about 300 to about 5000, alternatively fromabout 500 to about 4000, psi at 23° C. as determined by ASTM D412; atear strength of greater than about 300, alternatively greater thanabout 500, pli at 23° C. as determined by ASTM D624, Die C; and/or aTaber abrasion resistance of from about 25 to about 100, alternativelyfrom about 35 to about 85, mg when tested in accordance with ASTM D1044.

It is contemplated that the antifouling TPU composition may include oneor more TPUs. When more than one TPU is included in the antifouling TPUcomposition, greater than one TPU meets the description of the TPUs setforth above, and the additional TPUs are not limited to any particularTPU.

In one embodiment, a single, polyether-based TPU is present in theantifouling TPU composition in an amount of from about 70 to about 85parts by weight per 100 parts by weight of the antifouling TPUcomposition. In this embodiment, the polyether-based TPU has a Shore DHardness of from about 51 to about 55 and a specific gravity of fromabout 1.15 to about 1.17.

In various embodiments, the antifouling TPU composition includes acompound, an oligomer, a polymer, etc., which includes silicon and/orhalogen atoms. In other words, in various embodiments, the antifoulingTPU composition includes a mixture comprising the TPU and a compound, anoligomer, and/or a polymer which includes silicon and/or halogen atoms.

For example, in some embodiments, the antifouling TPU compositionincludes a silicone, a polysiloxane, a polyorganosiloxane, orcombinations thereof. In a preferred embodiment, the antifouling TPUcomposition includes an ultra high molecular weight polydimethylsiloxane(PDMS). Suitable silicones include, but are not limited to, siliconescommercially available from Multibase, a Dow Corning Corporation ofMidland, Mich. under the trade name MB Siloxane® Masterbatch.

As another example, in some embodiments, the antifouling TPU compositionincludes a halogenated polymer. In one such embodiment the antifoulingTPU composition includes a fluorinated polymer. The fluorinated polymermay be, for example, selected from the group of a polyvinyl fluoridepolymer, a polyvinylidene fluoride polymer, a vinylidenefluoride/hexafluoropropylene copolymer, atetrafluoroethylene/hexafluoropropylene/vinylidene fluoride typecopolymer, a tetrafluoroethylene/propylene copolymer, atetrafluoroethylene/hexafluoropropylene/propylene copolymer, anethylene/tetrafluoroethylene type copolymer, anethylene/chlorotrifluoroethlyene copolymer, ahexafluoropropylene/tetrafluoroethylene copolymer, a perfluoro(alkylvinyl ether)/tetrafluoroethylene type copolymer, and combinationsthereof. In certain embodiments, the fluorinated polymer is selectedfrom the group of an ethylene/tetrafluoroethylene copolymer, anethylene/chlorotrifluoroethlyene copolymer, a polyvinyl fluoride, apolyvinylidene fluoride, and combinations thereof. In other embodiments,the fluorinated polymer is selected from the group of anethylene/tetrafluoroethylene copolymer, anethylene/chlorotrifluoroethlyene copolymer, and combinations thereof. Inone specific embodiment, the fluorinated polymer comprises anethylene/tetrafluoroethylene copolymer, and in another specificembodiment, the fluorinated polymer comprises anethylene/chlorotrifluoroethlyene copolymer.

In various embodiments, the antifouling TPU composition includes anantifouling additive, e.g. a biocide. Of course, the antifouling TPUcomposition can include one or more different types of the antifoulingadditive. The antifouling additive helps prevent the build-up oforganisms such as marine species, including micro-foulers (which arefood sources for the macrofoulers), on the article.

The one or more antifouling additives can be biocidal, foul release, orboth. Exemplary biocidal antifouling additives include, but are notlimited to, metal or metallic/non-metallic compounds that are poisonousto marine organisms and thus prevent or reduce biofouling by making itdifficult for marine organisms to survive when in contact with thearticle. Illustrative foul release antifouling additives include, butare not limited to, silicon or halogenated compounds that reduce thesurface energy of the article and thus prevent or reduce the ability ofmarine organisms to attach thereto.

Marine organisms as defined herein include, but are not limited to,“soft fouling organisms,” which can include plants and invertebrates,such as slime, algae, kelp, soft corals, tunicates, hydroids, spongesand anemones; or “hard fouling organisms,” which can includeinvertebrates having some type of hard outer shell, such as barnacles,tubeworms and molluscs.

The antifouling additive can be a metal or metal alloy. The metal ormetal alloy can include any one or more metals from groups Ib, IIa, IIb,Ma, Mb, IVa, IVb, Va, Vb, VIb, VIIb, and VIII of the Periodic Table ofElements. The antifouling additive can include, but is not limited to,copper, nickel, palladium, platinum, tantalum, tellurium, titanium,beryllium, magnesium, manganese, calcium, silver, gold, zinc, cadmium,mercury, boron, aluminum, molybdenum, scandium, yttrium, silicon,zirconium, tin, arsenic, alloys thereof, and combinations thereof. Themetal alloy can be or include, for example, copper-nickel alloy,copper-beryllium alloy, beryllium-cobalt-copper alloy,beryllium-cobalt-silicon-copper alloy, or combinations thereof.

Suitable exemplary antifouling additives include, but are not limitedto, inorganic compounds. The antifouling additive can be or includeoxides, carbonates, halides, hydroxides, cyanides, nitrates, nitrites,nitrides, sulfates, sulfites, sulfides, or combinations thereof of ametal or metal alloy. In one or more embodiments, the antifoulingadditive can be or include, oxides, carbonates, halides, hydroxides,cyanides, nitrates, nitrites, nitrides, sulfates, sulfites, or sulfidesof copper, nickel, palladium, platinum, tantalum, tellurium, titanium,beryllium, magnesium, manganese, calcium, silver, gold, zinc, cadmium,mercury, boron, aluminum, molybdenum, scandium, yttrium, silicon,zirconium, tin, arsenic, lead, oxides thereof, alloys thereof, andcombinations thereof.

Suitable exemplary antifouling additives include, but are not limitedto, products of reaction between a metal or metal compound and a resinacid. The resin acid can be or include abietic acid, pimaric acid,neoabietic acid, dehydroabietic acid, palustric acid, levopimaric acid,isopimaric acids, derivatives thereof, and mixtures thereof. Forexample, the antifouling additive can be or include products of reactionbetween copper or a copper compound and rosin, or products of reactionbetween tin or a tin compound and rosin.

Suitable exemplary antifouling additives include, but are not limitedto, organometallic compounds. The antifouling additive can be or includeorganotin compounds. In one or more embodiments, the organotin compoundscan include, but are not limited to, a trialkyl tin, triaryl tin, orboth. Illustrative examples of organotin compounds can be or includebistributyl tin oxide, tributyl tin chloride, tributyl tin fluoride,tributyl tin acetate, tributyl tin nicotinate, tributyl tin versatate,bistributyl tin, triphenyl tin hydroxide, bistriphenyl tinalpha-dibromosuccinate, bistriphenyl tin oxide, bistryphenyl tinmonochloromaleinate, and other organotin compounds.

Suitable exemplary antifouling additives include, but are not limitedto, organocopper compounds. In one or more embodiments, the organocoppercompounds can include, but are not limited to, copper acetate, oxinecopper, copper nonylphenolsulfonate, copperbis(ethylenediamine)-bis(dodecylbenzenesulfonate), copper naphthenate,copper bis(pentachlorophenolate), copper pyrithione, copper naphtenate,and derivatives thereof.

Suitable exemplary antifouling additives include, but are not limitedto, other organometallic compounds, which can include, but are notlimited to, organonickel compounds, such as nickel acetate and nickeldimethyldithiocarbamate; organozinc compounds, such as zinc acetate,zinc carbamate, bis(dimethylcarbamoyl) zincethylene-bis(dithiocarbamate), zinc dimethyldithiocarbamate, zincpyrithione, and zinc ethylene-bis(dithiocarbamate); and mixedmetal-containing organic compounds such as (polymeric) manganeseethylene bis dithiocarbamate complexed with zinc salt (mancozeb), andderivatives thereof. In a preferred embodiment, the antifouling additivecomprises zinc pyrithione which has the following general structure:

Suitable exemplary antifouling additives include, but are not limitedto, alpha-dibromosuccinate; biocidal metal carboxylates such as coppernaphthenate or copper stearate; metal (e.g. Na, K, Zn, Pb, Cu, Fe, Ni,Mg, Se) dialkyl dithiocarbamates such as zinc dimethyl dithiocarbamateand thiuram disulfide; sulfamides such as phthalylsulfathiazole,sulfaethydrole, sulfanilidopyridine or sulfamethoxyine; pyrrole andimidazole compounds such as glyodine, fentizole or polycide; thioxaneand thioxanthone compounds such as terazol, asterol or mylone; amidessuch as nicarbazin, 3,4,5-tribromosalicylanilide,N-trichloromethyl-mercaptophthalimide or 3,5-dinitrobenzamide;polyhexamethyleneguanidine salts; and derivatives thereof.

Suitable exemplary antifouling additives include, but are not limitedto, a metal-free organic compound, such asN-trihalomethylthiophthalimides, trihalomethylthiosulphamides,dithiocarbamic acids, N-arylmaleimides, 3-(substituted amino)-1,3thiazolidine-2,4-diones, dithiocyano compounds, triazine compounds,oxathiazines, 2,4,5,6-tetrachloroisophthalonitrile,N,N-dimethyl-dichlorophenylurea,4,5-dichloro-2-n-octyl-4-isothiazoline-3-one,N,N-dimethyl-N′-phenyl-(N-fluorodichloromethylthio)-sulfamide,tetramethylthiuram di sulphide, 3-iodo-2-propinylbutyl carbamate,2-(methoxycarbonylamino)benzimidazole, 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine, diiodomethyl-p-tolyl sulphone,phenyl(bispyridine)bismuth dichloride, 2-(4-thiazolyl)benzimidazole,dihydroabietyl amine, N-methylol formamide and pyridine triphenylborane,and others.

Suitable exemplary antifouling additives include, but are not limitedto, one or more pesticides. The pesticide can be or include one or morefungicides, herbicides, insecticides, algicides, molluscicides,bacteriocides, or combinations thereof. The fungicide can be or includealiphatic nitrogen fungicides, such as butylamine, cymoxanil, dodicin,dodine, guazatine, and iminoctadine; amide fungicides, such as bixafen,carpropamid, chloraniformethan, cyflufenamid, diclocymet, ethaboxam,fenoxanil, flumetover, furametpyr, mandipropamid, penthiopyrad,prochloraz, quinazamid, silthiofam and triforine; acylamino acidfungicides, such as benalaxyl, benalaxyl-M, furalaxyl, metalaxyl,metalaxyl-M and pefurazoate; anilide fungicides, such as benalaxyl,benalaxyl-M, boscalid, carboxin, fenhexamid, isotianil, metalaxyl,metalaxyl-M, metsulfovax, ofurace, oxadixyl, oxycarboxin, pyracarbolid,thifluzamide and tiadinil; benzanilide fungicides, such as benodanil,flutolanil, mebenil, mepronil, salicylanilide and tecloftalam;furanilide fungicides, such as fenfuram, furalaxyl, furcarbanil andmethfuroxam; sulfonanilide fungicides, such as flusulfamide; benzamidefungicides, such as benzohydroxamic acid, fluopicolide, fluopyram,tioxymid, trichlamide, zarilamid, zoxamide; furamide fungicides, such ascyclafuramid and furmecyclox; phenylsulfamide fungicides, such asdichlofluanid and tolylfluanid; sulfonamide fungicides amisulbrom andcyazofamid; valinamide fungicides, such as benthiavalicarb andiprovalicarb; antibiotic fungicides, such as aureofungin, blasticidin-S,cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxins,polyoxorim, streptomycin and validamycin; strobilurin fungicides, suchas azoxystrobin, dimoxystrobin, fluoxastrobin. kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin andtrifloxystrobin; aromatic fungicides, such as biphenyl,chlorodinitronaphthalene, chloroneb, chlorothalonil, cresol, didoran,hexachlorobenzene, pentachlorophenol, quintozene, sodiumpentachlorophenoxide and tecnazene; benzimidazole fungicides, such asbenomyl, carbendazim, chlorfenazole, cypendazole, debacarb,fuberidazole, mecarbinzid, rabenzazole and thiabendazole; benzimidazoleprecursor fungicides, such as furophanate, thiophanate andthiophanate-methyl; benzothiazole fungicides, such as bentaluron,chlobenthiazone and TCMTB; bridged diphenyl fungicides, such asbithionol, dichlorophen and diphenylamine; carbamate fungicides, such asbenthiavalicarb, furophanate, iprovalicarb, propamocarb, pyraclostrobin,pyribencarb, thiophanate and thiophanate-methyl; benzimidazolylcarbamatefungicides, such as benomyl, carbendazim, cypendazole, debacarb andmecarbinzid; carbanilate fungicides, such as diethofencarb; conazolefungicides (imidazoles), such as climbazole, clotrimazole, imazalil,oxpoconazole, prochloraz, and triflumizole; conazole fungicides(triazoles), such as azaconazole, bromuconazole, cyproconazole,diclobutrazol, difenoconazole, diniconazole, diniconazole-M,epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole,flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, quinconazole, simeconazole, tebuconazole,tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole anduniconazole-P; copper fungicides, such as Bordeaux mixture, Burgundymixture, Cheshunt mixture, copper acetate, copper carbonate, basic,copper hydroxide, copper naphthenate, copper oleate, copper oxychloride,copper silicate, copper sulfate, copper sulfate, basic copper zinc,chromate, cufraneb, cuprobam, cuprous oxide, mancopper and oxine-copper;dicarboximide fungicides, such as famoxadone and fluoroimide;dichlorophenyl dicarboximide fungicides, such as chlozolinate,dichlozoline, iprodione, isovaledione, myclozolin, procymidone andvinclozolin; phthalimide fungicides, such as captafol, captan,ditalimfos, folpet and thiochlorfenphim; dinitrophenol fungicides, suchas binapacryl, dinobuton, dinocap, dinocap-4, dinocap-6, meptyldinocap,dinocton, dinopenton, dinosulfon, dinoterbon and DNOC; dithiocarbamatefungicides, such as azithiram, carbamorph, cufraneb, cuprobam,disulfuram, ferbam, metam, nabam, tecoram, thiram and ziram; cyclicdithiocarbamate fungicides, such as dazomet, etem and milneb; polymericdithiocarbamate fungicides, such as mancopper, mancozeb, maneb, metiram,polycarbamate, propineb and zineb; imidazole fungicides, such ascyazofamid, fenamidone, fenapanil, glyodin, iprodione, isovaledione,pefurazoate and triazoxide; inorganic fungicides, such as potassiumazide, potassium thiocyanate, sodium azide and sulfur; mercuryfungicides, such as mercuric chloride, mercuric oxide and mercurouschloride; organomercury fungicides, such as (3-ethoxypropyl)mercurybromide, ethylmercury acetate, ethylmercury bromide, ethylmercurychloride, ethylmercury 2,3-dihydroxypropyl mercaptide ethylmercuryphosphate, N-(ethylmercury)-p-toluenesulphonanilide, hydrargaphen,2-methoxyethylmercury chloride, methylmercury benzoate, methylmercury,icyandiamide, methylmercury pentachlorophenoxide,8-phenylmercurioxyquinoline, phenylmercuriurea, phenylmercury acetate,phenylmercury chloride, phenylmercury derivative of pyrocatechol,phenylmercury nitrate, phenylmercury salicylate, thiomersal andtolylmercury acetate; morpholine fungicides, such as aldimorph,benzamorf, carbamorph, dimethomorph, dodemorph, fenpropimorph, flumorphand tridemorph; organophosphorus fungicides, such as ampropylfos,ditalimfos, edifenphos, fosetyl, hexylthiofos, iprobenfos, phosdiphen,pyrazophos, tolclofos-methyl and triamiphos; organotin fungicides, suchas decafentin and fentin, tributyltin oxide; oxathiin fungicides, suchas carboxin and oxycarboxin; oxazole fungicides, such as chlozolinate,dichlozoline, drazoxolon, famoxadone, hymexazol, metazoxolon,myclozolin, oxadixyl and vinclozolin; polysulfide fungicides, such asbarium polysulfide, calcium polysulfide, potassium polysulfide andsodium polysulfide; pyrazole fungicides, such as bixafen, furametpyr,penthiopyrad, pyraclostrobin and rabenzazole; pyridine fungicides, suchas boscalid, buthiobate, dipyrithione, fluazinam, fluopicolide,fluopyram, pyribencarb, pyridinitril, pyrifenox, pyroxychlor andpyroxyfur; pyrimidine fungicides, such as bupirimate, cyprodinil,diflumetorim, dimethirimol, ethirimol, fenarimol, ferimzone,mepanipyrim, nuarimol, pyrimethanil and triarimol; pyrrole fungicides,such as fenpiclonil, fludioxonil and fluoroimide; quinoline fungicides,such as ethoxyquin and halacrinate, 8-hydroxyquinoline sulfate,quinacetol and quinoxyfen; quinone fungicides, such as benquinox,chloranil, dichlone and dithianon; quinoxaline fungicides, such aschinomethionat, chlorquinox and thioquinox; thiazole fungicides, such asethaboxam, etridiazole, metsulfovax, octhilinone, thiabendazole,thiadifluor and thifluzamide; thiocarbamate fungicides, such asmethasulfocarb and prothiocarb; thiophene fungicides, such as ethaboxamand silthiofam; triazine fungicides, such as anilazine; triazolefungicides, such as amisulbrom, bitertanol, fluotrimazole, andtriazbutil; urea fungicides, such as bentaluro, pencycuron, andquinazamid; and unclassified fungicides, such as acibenzolar, acypetacs,allyl alcohol, benzalkonium chloride, benzamacril, bethoxazin, carvone,chloropicrin, DBCP, dehydroacetic acid, diclomezine, diethylpyrocarbonate, fenaminosulf, fenitropan, fenpropidin, formaldehyde,furfural, hexachlorobutadiene, iodomethane, isoprothiolane, methylbromide, methyl isothiocyanate, metrafenone, nitrostyrene,nitrothal-isopropyl, OCH, 2-phenylphenol, phthalide, piperalin,probenazole, proquinazid, pyroquilon, sodium orthophenylphenoxide,spiroxamine, sultropen, thicyofen, tricyclazole, zinc naphthenate, ormixtures thereof.

Suitable exemplary antifouling additives include, but are not limitedto, pesticides such as carboxylic acid derivatives, which can includebenzoic acids and their salts, phenoxy and phenyl substituted carboxylicacids and their salts, and trichloroacetic acid and its salts; carbamicacid derivatives, which can include ethyl N,N-di(n-propyl)thiolcarbamateand pronamide; substituted ureas; substituted triazines; diphenylethers, which can include oxyfluorfen and fluoroglycofen; anilides suchas propanil; oxyphenoxy herbicides; uracils; nitriles; and other organicherbicides such as dithiopy and thiazopyr.

Suitable exemplary antifouling additives include, but are not limitedto, insecticides such as acephate, acethion, acetoxon, aldicarb,aldoxycarb, aldrin, allethrin, allyxycarb, alpha-cypermethrin,amidithion, amitraz, amlure, anethol, azethion, azinphos-ethyl,azinphos-methyl, azocyclotin, Bacillus thuringiensis, BCPE, bendiocarb,bensultap, benzoximate, benzyl acetate, benzyl benzoate, BHC,bifenthrin, binapacryl, bornyl, BPMC, bromophos, bromophos-ethyl,bromopropylate, bufencarb, buprofezin, butacarb, butocarboxim, butonate,butoxycarboxim, calcium arsenate, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, chlordane, chlordecone, chlordimeform,chlorfenethol, chlorfenson, chlorfensulphide, chlorfenvinphos,chlormephos, chlorobenzilate, chloropenozide, chloropropylate,chlorphoxim, chlorpyrifos, chlorpyrifos methyl, chlorthiophos,clofentezine, CPCBS, CPMC, crotoxyphos, crufomate, cryolite, cufraneb,cyanofenphos, cyanophos, cyanthoate, cyfluthrin, cyhexatin,cypermethrin, cyphenothrin, cyromazine, DAEP, DDT, DDVP, deltamethrin,demeton, demeton-5-methyl, demeton-O-methyl, demeton-S, demeton-5-methylsulfoxid, demephion-O, demephion-S, dialifor, diazinon, dicapthon,dichlofenthion, dicofol, dicrotophos, dieldrin, dienochlor,diflubenzuron, dihydrorotenone, dimefox, dimetan, dimethoate, dimethrin,dinex, dinitrophenol, dinobuton, dinocap, dioxabenzofos, dioxacarb,dioxathion, disparlure, disulfoton, DMCP, DNOC, d-trans allethrin,endosulfan, endothion, endrin, entice, EPBP, EPN, esfenvalerate,ethiofencarb, ethion, ethoate-methyl, ethoprop, etrimfos, fenamiphos,fenazaflor, fenbutatin-oxide, fenitrothion, fenoxycarb, fenpropathrin,fenson, fensulfothion, fenthion, fenvalerate, flubenzimine,flucythrinate, fluenethyl, flufenoxuron, fluvalinate, fonofos,formetanate hydrochloride, formothion, fosmethilan, fosthietan,furathiocarb, furethrin, grandlure, heptachlor, HETP, hexythiazox,hydramethylnon, hydroprene, IPSP, isazophos, isobenzan, isofenphos,isoprocarb, isoprothiolane, isothioate, isoxathion, jodfenphos,kinoprene, lead arsenate, leptophos, lethane, lindane, lythidathion,malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan,methamidophos, methidathion, methiocarb, methomyl, methoprene,methoxychlor, methoxyfenozide, methyl parathion, methyl phencapton,mevinphos, mexacarbate, MIPC, mirex, monocrotophos, MTMC, naled,nicotine, nonachlor, omethoate, ovex, oxamyl, oxydeprofs, oxydisulfoton,oxythioquinox, paraoxon, parathion, paris green, permethrin, perthane,phencapton, phenthoate, phorate, phosalone, phosfolan, phosmet,phosnichlor, phosphamidon, phoxim, pirimicarb, pirimiphos-ethyl,pirimiphos-methyl, plifenate, profenofos, promecarb, propargite,propetamphos, propoxur, prothidathion, prothiophos, prothoate, PTMD,pyridaben, pyridaphenthion, quinalphos, resmethrin, ronnell, rotenone,ryania, s-bioallethrin, salithion, schradan, sodium fluosilicate,sophamide, sulfotepp, sulprofos, tebufenozide, tefluthrin, temephos,TEPP, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetrasul,thallium sulfate, thiocarboxime, thiocyclam hydrogenoxalate, thiometon,tolclofos-methyl, toxaphene, triazamate, triazophos, trichlorfon,trichloronate, triflumuron, trimethacarb, vamidothion, and xylylcarb,and mixtures thereof.

Suitable exemplary antifouling additives include, but are not limitedto, algicides such as 3-bethoxazin, copper(II) tetraoxosulfate,cybutryne, dichlone, dichlorophen, endothal, fentin, calcium hydroxide,nabam, quinoclamine, quinonamid, and simazine.

Suitable exemplary antifouling additives include, but are not limitedto, molluscicides such as N-bromoacetamide, calcium arsenate,cloethocarb, copper acetoarsenite, copper sulfate, fentin, metaldehyde,methiocarb, niclosamide, pentachlorophenol, sodium pentachlorophenolate,tazimcarb, thiodicarb, tralopyril, bis(tributyltin) oxide, trifenmorph,trimethacarb.

Suitable exemplary antifouling additives include, but are not limitedto, bacteriocides such as 2-bromo-2-nitropropane-1,3-diol, copper(II)hydroxide, methylphenol, 4,4′-dichloro-2,2′-methylenediphenol,di-2-pyridyl disulfide 1,1′-dioxide,N-[2-(2-dodecylaminoethylamino)ethyl]glycine, sodium(EZ)-4-dimethylaminobenzenediazosulfonate, formaldehyde,μ-(2,2′-binaphthalene-3-sulfonyloxy)bis(phenylmercury),bis(8-hydroxyquinolinium) sulfate (“8-hydroxyquinoline sulfate”),1L-1,3,4/2,5,6-1-deoxy-2,3,4,5,6-pentahydroxycyclohexyl2-amino-2,3,4,6-tetradeoxy-4-α-iminoglycino)-α-D-arabino-hexo-pyranoside,2-chloro-6-trichloromethylpyridine, 2-octyl-1,2-thiazol-3(2H)-one,5-ethyl-5,8-dihydro-8-oxo[1,3]dioxolo[4,5-g]quinoline-7-carboxylic acid,(4S,4aR,5S,5aR,6S,12aS)-4-dimethylamino-1,4,4a,5,5a,6,11,12a-octahydro-3,-5,6,10,12,12a-hexahydroxy-6-methyl-1,11-dioxonaphthacene-2-carboxamide,3-allyloxy-1,2-benzothiazole 1,1-dioxide,O-2-deoxy-2-methylamino-α-L-glucopyranosyl-(1-2)-O-5-deoxy-3-C-form-yl-α-L-lyxofuranosyl-(1-4)-N.sup.1,N.sup.3-diamidino-D-streptamine,2′,3,3′,4,5,6-hexachlorophthalanilic acid, and sodium salt of(2-carboxyphenylthio)ethylmercury.

Suitable exemplary antifouling additives include, but are not limitedto, 5-chloro-2-(2,4-dichlorophenoxy)phenol; 2-phenylphenol;benzisothiazolinone; bromine monochloride; manganeseethylenebisdithiocarbamate; zinc dimethyl dithiocarbamate;2-methyl-4-t-butylamino-6-cyclopropylamino-s-triazine;2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyl dichlorophenyl urea;zinc ethylenebisdithiocarbamate; copper thiocyanate; copper pyrithione;zinc pyrithione; chlorinated paraffin;4,5-dichloro-2-n-octyl-3-isothiazolone;N-(fluorodichloromethylthio)-phthalimide;N,N-dimethyl-N′-phenyl-N′-fluorodichloromethylthio-sulfamide; zinc2-pyridinethiol-1-oxide; tetramethylthiuram di sulfide;2,4,6-trichlorophenylmaleimide;2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine; 3-iodo-2-propynyl butylcarbamate; diiodomethyl p-tolyl sulfone; bis dimethyl dithiocarbamoylzinc ethylenebisdithiocarbamate; phenyl (bispyridil) bismuth dichloride;2-(4-thiazolyl)-benzimidazole; pyridine triphenyl borane; phenylamidecompounds; pyridazinone compounds; or 2-haloalkoxyaryl-3-isothiazolones;derivatives thereof, and mixtures thereof.

Suitable exemplary antifouling additives include, but are not limitedto, polyhydroxystyrene of the novolak type; (meth)acrylic acid and oneor more (meth)acrylate or (meth)acrylamide; menadione triaminotriazinebisulfite(I) (“MTB”); menadione(bis) piperazine bisulfite(II) (“MBP”);3-aryl-5,6-dihydro-1,4,2-oxathiazines and oxides thereof; 2-arylpyrrole;3′,4′-dichlorodecananilide; 3′,5′-dichlorodecanailide;3′,4′-dichloro-3-chloropropaneanilide;N-(3,4-dichlorophenyl)heptanamide; octanilide;N-(3,4-dichlorophenyl)octanamide; N-(3,4-dichlorophenyl)hexanamide;2-chloro-2′,6′-diethyl-N-(methoxymethyl)acetanilide;1,3-dithiolo(4,5-d)-1,3-dithiino-2-thione compounds; a lipid enzymecoated with 6 to 30 carbon atoms; one or more of4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,2-n-octyl-4-isothiazolin-3-one, and salts thereof mixed with one or morecompounds selected from 5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole and octachlorodipropylether; 4,5-dicyano-1,3-dithiole-2-one (or thione) containing oxygen orsulfur; 1,2,5-thiadiazolo-1,3-dithiole-2-one or thione;3,5-dihalogeno-1,2,6-thiadiazin-4-one; hydantoin and substitutedhydantoin, such as phenyloin; dichloro-s-triazinetrione,trichloro-s-triazinetrione; zinc dimethyldithiocarbamate; manganeseethylenebisdithiocarbamate;2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine;2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyl dichlorophenylurea;4,5-dichloro-2-n-octyl-3(2H)-isothiazolone;N-(fluorodichloromethylthio)-phthalimide;N,N′-dimethyl-N′-phenyl-(N-fluorodichloromethylthio)sulfamide;2,4,6-trichlorophenylmaleimide;2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 3-iodo-2-propenylbutylcarbamate; diiodomethyl-p-tolylsulfone; dimethyldithiocarbamoylzincethylenebisdithiocarbamate; phenyl(bispyridine)bismuth dichloride;2-(4-thiazolyl)benzimidazole; pyridine-triphenylborane; zincethylenebisdithiocarbamate; stearylamine-triphenylboron; andlaurylamine-triphenylboron; 3-iodo-2-propynyl butyl carbamate;5-chloro-2-(2,4-dichlorophenoxy)phenol; 3,4,4′-trichlorocarbanilide;derivatives thereof; and mixtures thereof.

Suitable exemplary antifouling additives include, but are not limitedto, one or more isothiazolones, furanones, and combinations thereof. Theantifouling additive can be 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.The antifouling additive can be(1′RS,5E)-3-(1′-Bromoethyl)-4-bromo-5-(bromomethylidene)-2(5H)-furanone;(1′RS)-3-(1′-Bromoethyl)-5-(dibromomethylidene)-2(5H)-furanone;(1′RS,5Z)-3-(1′-Bromohexyl)-4-bromo-5-(bromomethylidene)-2(5H)-furanone;and (1′RS)-3-(1′-Bromohexyl)-5-(dibromomethylidene)-2(5H)-furanone.

Suitable exemplary antifouling additives include, but are not limitedto, a chlorinated organotin compound. Exemplary chlorinated organotincompounds include, but are not limited to, is-trialkylstannylderivatives of chlorinated polycyclic dicarboxylic acids.

Suitable exemplary antifouling additives include, but are not limitedto, antibiotics. Exemplary antibiotics include, but are not limited to,penicillin V, penicillin G, ampicillin, cephalosporin,chlortetracycline, neomycin, rifamycin, and variotin.

Suitable exemplary antifouling additives include, but are not limitedto, a metal containing acrylic resin. The metal containing acrylic resincan include various substances, for example, inorganic compounds,metal-containing organic compounds and metal-free organic compounds.Illustrative examples of various substances which can be included in ametal containing acrylic resin include, but are not limited to, cuprousoxide, manganese ethylenebisdithiocarbamate, zinc dimethylcarbamate,2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,2,4,6-tetrachloroisophthalonirile, N,N-dimethyldicholorophenylurea, zincethylenebisdithiocarbamate, copper rhodanate,4,5-dichloro-2-n-octyl-3(2H)-isothiazolone,N-(fluorodichloromethylthio)phthalimide,N,N′-dimethyl-N′-phenyl-(N-fluorodichloromethylthio)sulfamide,2-pyridinethiol-1-oxide zinc salt and copper salt, tetramethylthiuramdisulfide, 2,4,6-trichlorophenylmaleimide,2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 3-iodo-2-propylbutylcarbamate, diiodomethyl-p-tolyl sulfone, phenyl(bispyridyl)bismuthdichloride, 2-(4-thiazolyl)-benzimidazole, triphenylboron pyridine saltand so forth.

In one or more embodiments, suitable exemplary antifouling additivesinclude, but are not limited to, one or more geometrical isomers of anacrylonitrile compound, an acylonitrile salt, or mixtures thereof.

In one or more embodiments, suitable exemplary antifouling additivesinclude, but are not limited to, one or more capsicum derivatives.Illustrative capsicum derivatives can include8-methyl-N-vanillyl-6-nonenamide (“capsaicin”),N-(4-Hydroxy-3-methoxybenzyl)-8-methylnonanamide (“dihydrocapsaicin”),N-(4-Hydroxy-3-methoxybenzyl)-7-methyloctanamide(“nordihydrocapsaicin”),N-(4-Hydroxy-3-methoxybenzyl)-9-methyldecanamide(“homodihydrocapsaicin”),(3E)-N-(4-Hydroxy-3-methoxybenzyl)-9-methyldec-7-enamide(“homocapsaicin”), and N-(4-hydroxy-3-methoxy-benzyl)nonanamide(“nonivamide”). Illustrative derivatives of capsaicin can includecayenne pepper and oleoresin capsicum. In one or more embodiments, thecapsicum derivatives can be mixed or otherwise combined with otherantifouling additives.

Suitable exemplary antifouling additives include, but are not limitedto, silver acetate and silver citrate; quaternary amine compounds, suchas cetrimide; isoniazid; benzalkonium chloride; sulfa-basedantimocrobial compounds such as sulfanilamide, sulfaguanidine,sulfathiazole, sulfacetamide, sulfabenzamide and sulfamethiazole;cholesterol; saponins, and sapotoxins. Suitable antifouling additivesare commercially available from BASF Corporation of Florham Park, N.J.under the trade name Irgarol®.

Suitable exemplary antifouling additives include, but are not limitedto, a bio-jelly. Bio-jelly growth can be promoted by compounds which caninclude 1,8-cineole, benzylidene aniline derivatives and compoundshaving styrene or cinnamolyl groups.

Illustrative examples of bio-jelly producing additives can be4′-ethylbenzylidene-4-ethyl aniline,2′-isopropylbenzylidene-4-butoxyaniline, 4-nonyl benzylideneaniline,4′-stearylbenzylidene-4-butoxyaniline, benzylidene-4-nonyloxyaniline,4′-ethylbenzylidene-4-hexylaniline,4′-ethoxybenzylidene-4-n-octylaniline,2′-butoxybenzylidene-2-ethylaniline, 4′-naphthyloxy benzylidene aniline,4′-ethylbenzylidene-4-nitroaniline,3′,4′-diethylbenzylidene-4-butylaniline,terephthalidene-di-4-butoxyaniline,di-4-butoxybenzylidene-p-phenylenediamine, benzylidene-4-n-octylaniline,4′-nonylbenzylidene-4-methoxyaniline, 4′-ethylhexylbenzylideneaniline,4′,4-oleyloxybenzylideneaniline, 2′-ethoxy-4′-bromobenzylideneaniline,4′-hexylbenzylidene-4-octoxyaniline,4′-nonyloxybenzylidene-4-nonylaniline,4′-nonylbenzylidene-2-butoxyaniline, benzylideneoctylamine,butylideneaniline, octylidene-4-hexylaniline, octylidene-4-octylaniline,cinnamilideneaniline and cinnamilideneoctylamine, benzylidene aniline,benzylidene-4-chloroaniline, benzylidene-4-bromoaniline,benzylidene-4-nitroaniline, benzylidene-4-hydroxyaniline,4′-methylbenzylideneaniline, 4′-chloro benzylideneaniline,2′-hydroxybenzylideneaniline, 2-methylpyridine, 4-ethylpyridine,4-hexylpyridine, 4-octylpyridine, 4-nonylpyridine, 4-decylpyridine,4-laurylpyridine, aniline, 4-ethylaniline, 4-hexylaniline,4-octylaniline, 4-nonylaniline, 4-decylaniline, 4-dodecylaniline,4-ethylnitrobenzene, 4-octyl benzenesulfonic acid,4-ethylbenzenesulfonic acid, 4-hexylnitrobenzene, 4-octylbenzaldehyde,4-nonylbenzaldehyde, 4-ethylbenzenesulfonic acid, 2-octylbenzoic acid,4-hexyloxy aniline, 4-nonyloxypyridine, 4-hexyl-2-chloro aniline,4-ethoxy-2-chloroaniline, 4-nonyloxyaniline, 4-decylbenzoic acid,4-oleylaniline and 4-stearylaniline.

Suitable exemplary antifouling additives include, but are not limitedto, a non-tin-containing, water-insoluble, organo or inorganic compoundselected from the group consisting of heterocyclic compounds, aromaticcompounds substituted with heteroatom substitutents, amino compounds,carbocyclic vinyl ether ketones, phospho compounds, polychlorinatedcarbocyclic and acyclic compounds, chlorinated carbocyclic carboxylates,copper (cupric) oleate, alkyl dimethyl benzene, 2,4-d,α-chlorocrotylester, 2,3-dichloro-2-methylpropionic acid sodium salt,diphenylacetrontrile, n-dodecyl thiocyanate,ethyl-N,N-dipropylthiolcarbamate, ethyl-N,N-diisobutyl thiolcarbamate,ethylenebis(dithiocarbamato) zinc, ferric dimethyl-dithiocarbamate,isobornyl thiocyanoacetate, manganese ethylenebisdithiocarbamate, disodium ethylene bisdithiocarbamate, s-propylbutylethylthiocarbamate,piperonyl-bis(2-[2′-n-butoxy ethoxy]ethyl)acetal, piperonyl butoxidealpha[2-(2-n-butoxyethoxy)-ethoxy]-4,5-methylenedi oxy 2-propyltoluene,piperonyl cyclonen, 3′,4′-dichloropropionalide,ethylene-1,2-bis(thiocarbamoyldimethylthiocarbamoyldisulfide),5,6,7,8-tetrahydro-1-naphthyl methylcarbamate, 2-thiocyanoethyldodecanoate, tetramethylthiuram disulfide, tert-butyl 4 (or5)-chloro-2-methylcyclohexanecarboxylate, S-propyldipropylthiocarbamate,zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, antimonytartrate, antimony potassium tartrate, boric acid, ammonium sulfamate,4-allyl-2-methoxyphenol, 2,3-dichloro-1,4-napthoquinone,cetylpyridinium, chloride, diphenylamine, 2-chloro-N,N-diallylacetamide,cetyltrimethylammonium bromide, 2-isopropylamino-4-chloro-6-ethylaminotriazine, dimethoxythiophosphate derivative of diphenyl sulfide, ethyl4-chloro-alpha(4-chlorophenyl), alpha-hydroxy benzene acetate methyl,diethylamino, dimethoxythiophosphate derivative of pyrimidine,ethoxylated nonylphenol, unsymmetrical hydrazine derivative of succinicacid, allyl, methylhydroxy substituted cyclopententone ester ofdimethylpropenyl cyclopropane carboxylic acid, 2,5-dichloro, 3-aminobenzoic acid, cinnamic acid, 2-6-dichloro, 4-nitroaniline, dichloro,isopropenyl anilide, dodecylguanidine monoacetate, trichlorophenyl,acetic acid, diphenyl ether, chlorophenyl derivative of the isobutyricacid ester of hydroxyl acetonitrile, trihydroxybenzoic acid,3-indolacetic acid, 3,5-dichloro-N-(3,3-dimethylpropyne)benzamide,napthalene acetamide dimethyl ethylphenoxy-cyclohexyl-2-propynylsulfite, o-phenylphenol, phthalic acid, chlorophenyl-isopropyl, propynylcarbamate, N-phenyl, N-butynyl chloroacetamide, amino, chloro, phenylderivative of azacyclohexamine, N,N-diallyl-2-chloroacetamide,aminoacetic acid derivative of methylphosphonate, 3,5-dinitro,4-N,N-dipropylamino benzene sulfonamide, 2-chloro-2-propenyldiethylcarbamodithioate, acrolein phenylhydrazone, ammoniumsaccharinate, 2-allyl-4-hydroxy-3-methyl-2-cyclopenten-1-one ester of2,2-dimethyl-3-(2-methylpropenyl cyclopropanecarboxylic acid),4-allyl-2-methoxyphenol o-(allyloxy)phenyl methylcarbamate,2-(allylthio)-2-thiazoline,1,2,3,4,7,7-hexachloro-5,6-bis(chloromethyl)-2-norbornene,4-ethylamino-6-isopropylamino-2-methylthio-1,3,5-triazine,2-amino-3-chloro-1,4-napthoquinone, 3-amino-5-nitro-o-toluamide,3-amino-1,2,4-triazole,2-chloro-4-ethylamino-6-isopropylamino-S-triazine,4-chloro-m-chlorocarbanilate, 6-chloropiperonyl chrysanthemumate,N-butyl-N-ethyl-α,α,α-trifluoro-2-6-dinitro-p-toluidine-,bis(p-chlorophenyl)-3-pyridine methanol, bis(dialkylphosphinothioyl)disulfide, bis(4-hydroxyiminomethylpyridinum-1-methyl)ether dichloride,2,4-bis(3-methoxylpropylamino)-6-methylthio-S-triazinebis(pentachloro-2,4-cyclopentadien-1-yl),N-(4-bromo-3-chlorophenyl)-N′-methoxy-N′-methyl urea,5-(bromomethyl)-1,2,3,4,7,7-hexachloro-2-norbornene, S—(O,O-diisopropylphosphoro-dithionate of N-(2-mercaptoethyl)benzenesulfonamide,benzamidooxy-acetic acid,3-benzylideneamino-4-phenylthiazoline-2-thione,bis(p-chlorophenoxy)methane bis(4-chlorophenyl) disulfide, 1,1-bis(pochlorophenyl)ethane 1,1-bis(p-chlorphenyl)-ethanol,o,o-dimethyl-o-2,5-dichloro-4-bromophenylthionophosphate,O,O-dimethyl-2,2,2-trichloro-1-n-butyryloxyethyl phosphonate, N-butylacetanilide, 2-tert-butylamino-4-chloro-6-ethylamino-5-triazine,2-tert-butylamino-4-ethylamino-6-methylmercapto-S-triazine,4-tert-butyl-2-chlorophenylmethyl methylphosphoramidite,o-(4-tert-butyl-2-chlorophenyl)o-methyl phosphoramidothionate, butyl3,4-dihydro-2,2-di methyl-4-oxo-1,2h-pyran-6-carboxylate,n-butyl-9-hydroxyfluorene-(9)-carboxylate,2-(p-tert-butylphenoxy)cyclohexyl 2-propynyl sulfite, 1-butyn-3-ylm-chlorophenyl-carbamate,N-trichloro-methylthio-4-cyclohexene-1,2-docarboximide, 1-napththyln-methyl carbamate,S-[[(p-chlorophenyl)thiol]methyl]O,O-diethylphosphorodithioate,2-chloro-N,N-diallyl-acetamide, 2-chloroallyl diethyl-dithiocarbamate,cetyldimethylethylammonium bromide, cetylpyridinium chloride,tetrachloro-p-benzoquinone, 2-chloro-4,6-bis(diethylamino)-s-triazine,p-chlorobenzyl p-chlorophenyl sulfide,1,2,3,5,6,-7,8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene,1-(3-chlorallyl)-3,5,7-triaza-1-azoniaadamantane chloride, ethyl4,4′-dichlorobenzylate, 5-chloro-2-benzothiazolethiol zinc salt,p-chlorobenzyl p-fluorophenyl sulfide, 1-chloro-N′-(3,4-dichlorophenyl)N,N-dimethylformamidine, 4-chloro-3,5-dimethyl phenoxy-ethanol,1,4-dichloro-2,5-dimethoxybenzene,1-(chloro-2-norbornyl)-3,3-dimethylurea, S-(p-chloro-α-phenylbenzyl)O,O-diethyl phosphorodithioate, p-chlorophenyl ester of benzene-sulfonicacid, N-3-chlorophenyl-1-(isopropyl-carbamoyl-1)-ethyl carbamate,3-(p-chlorophenyl)-5-methyl rhodanine, 4 (and 6)-chloro-2-phenylphenolsodium salt, p-chlorophenyl phenyl sulfone, 4-chlorophenyl2,4,5-trichloro-phenylazosulfide, N-(5-chloro-5-thiazolyl)propionamide,2-[4-chloro-o-tolyl)oxy]propionanilide,2-chloro-1-(2,4,5-trichloro-phenyl) vinyl dimethyl phosphate,N′-(4-chlorophenoxy)phenyl N,N-dimethylurea, isopropylN-(3-chlorophenyl) carbamate, copper 8-quinolinolate, 2-(2,4-dihydroxyphenyl)-1-cyclohexene-1-carboxylic acid-lactoneO,O-diethylphosphorothioate,2-chloro-4-dimethylamino-6-methylpyrimidine,3-(2-cyclopenten-1-yl)-2-methyl-4-oxo-2-cyclopenten-1-ylchrysanthemunate, α-cyclohexyl-α-phenyl-3-pyridyl-methanol,hydrochloride, N′-cyclo-octyl-N,N-dimethylurea,4′-dichlorocyclopropanecarboxanilide, 2,4-dichlorophenoxyacetic acid,3,5-dimethyl-1,3,5,2H-tetrahydrothiadiazine-2-thione, tetra-hydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione, 4-(2,4-dichlorophenoxy) butyricacid, dimethyl 2,3,5,6-tetra-chloroterephthalate,decyltriphenylphosphonium-bromochlorotriphenyl stannate, dehydroaceticacid (and its sodium salt), tris and bis(2,4-dichlorophenoxyethyl)phosphate, 2-methyl-thio-4-isopropylamino-6-methylamino-s-triazine,S-2,3-dichloroallyl N,N-diisopropyl thiolcarbamate,1,3-diaza-2,4-cyclopentadiene,N,N-di-n-butyl-p-chlorobenzene-sulfonamide 3,6-dichloro-o-anisic acid,O-(2-chloro-4-nitrophenyl) O,O-di methyl phosphorothioate,2,6-dichlorobenzonitrile, 2,3-dichloro-1,4-naphthoquinone,1,3-bis(1-hydroxy-2,2,2-trichloroethyl) urea, 3,4-dichlorobenzylmethylcarbamate (80%) mixture with 2,3-dichlorobenzyl methylcarbamate(20%), 1,1-dichloro-2,2-bis(p-ethylphenyl)ethane,2,4-dichloro-6-(o-chloro-anilino)-s-triazine,N-(dichlorofluoromethylthio)-N′N′-dimethyl-n-phenylsulfamide,4,4′-dichloro-N-methylbenzene-sulfoanilide, 2,6-dichloro-4-nitroaniline,2,5-dichloro-3-nitrobenzoic acid, 5,2′-dichloro-4′-nitro-salicylanilideethanol amine salt, 2′,5′-dichloro-4′-nitrososalicylanilide, 2,2′-dihydroxy-5,5′-dichlorophenyl methane,1-(2,4-dichlorophenoxyacetyl)-3,5-dimethylpyrazole, N-3,4-dichlorophenylN′-5-chloro-2-(2-sodium sulfonyl-4-chlorophenoxy)phenyl urea,2,4-dichlorophenyl ester of benzene sulfonic acid, 2,4-dichlorophenylmethanesulfonate, 2,4-dichlorophenyl 4-nitrophenyl ether4-dichlorotetrahydrothiophene 1,1-dioxide,4,4′-dichloro-alpha-trichloromethylbenzhydrol,3′,4′-dichloro-2-methacrylanilide (Diethoxyphosphinothioylthio)gamma-butyrolactone, O,O-diethyl s-carboethoxymethyl phosphorothioate,O,O-diethyl O-naphthylamido phosphorothioate, O,O-diethylO-3,5,6-trichloro-2-pyridyl phosphorothioate,2,2′-dihydroxy-3,5,3′,5′,4″-pentachlorotriphenylmethane 2″-sodiumsulfonate, O,O-diisopropyl s-diethyl dithiocarbamoyl phosphorodithioate,2,4-dimethylbenzyl2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate,O,O-dimethyl-S-2-(acetylamino)-ethyl dithiophosphate, N-dimethylaminosuccinamic acid,1,1-dimethyl-3-[3-(n-tert-butyl-carbamoyloxy)phenyl]urea, O,O-dimethyls-carboethoxymethyl phosphorothioate, O,O-dimethylO-(3-chloro-4-nitrophenyl) phosphorothioate,O,O-dimethyl-o-p-cyanophenyl phosphorothioate,o,o-dimethyl-s-[5-ethoxy-1,3,4-thiadiazol-2(3H)-onyl-(3)-methyl]phosphoro-dithioate,N,N-dimethyl-N′-(2-methyl-4-chlorophenyl)-formamidine hydrochloride,O,O-dimethyl o-(4-nitro-m-tolyl) phosphorothioate, o,s-dimethyltetrachloro thiotere-phthalate, 4′-dimethyltriazenoacetanilide,dinitrocyclohexylphenol, 2,4′-dinitro-4-trifluoromethyl diphenyl ether,2-(1-methyl-n-heptyl)-4,6-dinitrophenyl crotonate,N,N-dimethyl-2,2-diphenyl acetamide, diphenyl amine,2,6-dinitro-N,N-di-n-propyl-p-toluidine,di-n-propyl-2,5-pyridine-dicarboxylate,1,1′-ethylene-2,2′-dipyridiniumdibromide,2,3-dicyano-1,4-dithia-anthraquinone,3-(3,4-dichlorphenyl)-1,1-dimethyl-urea, n-dodecylguanidine acetate,2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate,ethoxymethylbis(p-chlorophenyl) carbinol,1,2-dihydro-6-ethoxy-2,2,4-trimethylquinone, 3-phenyl-1,1-dimethylureatrichloroacetate, O,O-dimethylS—(N-formyl-N-methylcarbamoyl-methyl)phosphorodithioate,2-formyl-4-chlorophenoxyacetic acid,3-furfuryl-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemunate,2-heptadecyl-2-imidazoline,7-chloro-4,6-dimethoxycoumaran-3-one-2-spiro-1′-(2′-methoxy-6′-methylcycl-ohex-2′-en-4′-one),1,1,1,3,3,3,-hexachloro-2-propanone,1,5a,6,9,9a,9b-hexahydro-4-a(4H)-dibenzofuran-carboxaldehyde,9-(p-n-hexyloxyphenyl)-10-methyl-acridinium chloride,2-hydroxymethyl-4-chloro-phenoxyacetic acid,N-hydroxy-methyl-2,6-dichlorothiobenzamide, Isopropyl N-phenylcarbamate,isobutyl triphenylmethylamine, 5-bromo-3-isopropyl-6-methyluracil,isopropyl-4,4′-diboromobenzilate, isopropyl 4,4′-dichlorobenzilate,isopropyl mercaptophenyl-acetate, O,O-dimethyl phosphorodithioate,3-cyclohexyl-6,7-dihydro-1H-cyclopentapyrimidine-2,4(3H,5H)-dione,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,S-[1,2-bis(ethoxy-carbonyl)ethyl]O,O-dimethyl phosphorodithioate,4-chloro-2-methylphenoxyacetic acid, 2-(4-chloro-2-methylphenoxy)propionic acid, sec-butyl 4 (or5)-chloro-2-methylcyclohexanecarboxylate,s-[(4,6-diamino-s-triazine-2-yl)methyl]O,O-dimethyl phosphorodithioate,2-isopropylamino-4-(3-methoxypropylamino)-6-methylthio-s-triazine,1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane,2-methoxy-4-isopropylamino-6-diethylamino-s-triazine,5-(N-methoxymethylcarbamoylmethyl) dimethyl phosphorothiolothiononate,alpha-methylbenzyl 3-(dimethoxy-phosphinyloxy)-cis-crotonate,m-(1-methyl butyl)phenyl methyl-carbamate,methyl-2-chloro-9-hydroxyfluorene-(9)-carboxylate,3,3′-methylenebis(4-hydroxycoumarin),2,2′-methylenebis(3,4,6-trichlorophenol),6-methyl-2-oxo-1,3-dithio(4,5-b)quinoxaline, O,O-dimethylS-(2,5-dichlorophenyl-thio)-methyl phosphorodithioate, 3(2-methylpiperidino)propyl-3,4-dichlorobenzoate, 4-(methylsulfonyl)-2,6-dinitro-n,n-dipropyl aniline,methyl-2,3,5,6-tetrachloro-n-methoxy-n-methylterephthalamate, O-methylO-(2,4,5-trichloro-phenyl) amidophosphorothiomate,3-(p-bromophenyl)-1-methyl-1-methoxyurea,1,2-dihydropyridazine-3,6-dione,3,3′-ethylenebis-(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazone-2-thione),S-ethyl hexahydro-1H-azepine-1-carbothioate,3-(p-chlorphenyl)-1,1-dimethylurea, 3-(p-chlorophenyl)-1,1-dimethylureatrichloroacetate, 1,2-dibromo-2,2-dichloroethyl dimethyl phosphate,beta-naphthoxyacetic acid,3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea,3-(hexahydro-4,7-methanoindan-5-yl)-1,1-dimethylurea,N-1-naphthyl-phthalamic acid, p-chlorophenyl p-phenyl4-chlorobenzenesulfonate, phenothiazine, ethyl mercapto-phenylacetateO,O-dimethyl-phosphorodithioate, n-phenyl-1-(ethylcarbamoyl-1)ethylcarbamate (d isomer), phosphoric acid,2-chloro-1-(2,4,5-trichlorophenyl)vinyl dimethyl ester,4-amino-3,5,6-trichloropicolinic acid, polychlorobenzoic acid,dimethylamine salt, 2,4-bis-(isopropylamino)-6-methoxy-s-triazine,2-methyl-mercapto-4,6-bis(isopropylamino)-s-triazine,2-chloro-n-isopropylacetanilide,2-chloro-4,6-bis(isopropyl-amino)-s-triazine,di-n-propyl-3-methyl-6,7-methylenedioxy-1,2,3,4-tetra-hydronaphthalene-1,-2-dicarboxylate,5-amino-4-chloro-2-phenyl-3(2H) pyridazinone, pyrethrin 1,8-quinolinol,dimethyl 2,4,5-trichlorophenyl phosphorothionate salicylanilide,1-(3,4-methylene-di oxyphenoxy)-3,6,9-trioxoundecane, sodium2-(2,4-dichlorophenoxy)ethyl sulfate,1-(2-methyl-cyclohexyl)-3-phenylurea, 1-(2,4,5-trichlorophenoxy)propionic acid, N′-chlor-2-methyl-p-valerotoluidide,1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene, methyl3,4-dichlorocarbanilate, 2,4,5-trichlorophenoxyacetic acid,trichlorobenzyl chloride, 2,2-bis(p-chlorophenyl)-1,1-dichloroethane,3-tert-butyl-5-chloro-6-methyluracil, 2,6-di-tert-butyl-p-tolyl methylcarbamate2,3,6,7-tetrachloro-4-a,8a-epoxy-1,2,3,4,4a,8a-hexahydro-14-methanonaphth-alene-5,8-dioneN-(1,1,2,2-tetrachloro-ethyl-sulfenyl)-cis-4-cyclohexene-1,2-dicarboximid-e,2,4,5,6-tetrachloroiso-phthalonitrile,1,2,4,5-tetrachloro-3-nitrobenzene, p-chlorophenyl 2,4,5-trichlorophenylsulfone, 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropane carboxylate,O,O,O′,O′-tetramethyl O,O′-thiodi-p-phenylene phosphorothioate,1,3,6,8-tetranitrocarbazole, 2-(4-thiazolyl)benzimidazole,2,2′-thiobis(4,6-dichlorophenol), 2,3-quinoxaline-dithiol cyclictrithiocarbonate, N-meta-tolyl phthalamic acid, S-2,3,3-trichloroallylN,N-di-isopropyl-thiolcarbamate, O,O-dimethyl(1-hydroxy-2,2,2-trichloroethyl)phosphonate, 2,3,6-trichlorobenzoicacid, trichlorobenoic acid, dimethyl amine salt,4,5,7-trichlorobenzthiadiazole-2,1,3,2,3,6-trichlorobenzyloxypropanol,N-trichloromethylthio-benzothiazolone,N-trichloromethylthiobenzoxazolone,2,2,2-trichloro-n-(pentachloro-phenyl)acetimidoyl chloride,2-(2,4,5-trichlorophenoxy)ethyl sulfate, sodium salt,N,N′-N″-trichloro-2,4,6-triamine-1,3,5-triazine,2-chloro-4-(di-ethylamino)-6-(ethylamino)-s-triazine,3,5-dinitro-o-toluamide, and mixtures thereof.

Suitable antifouling additives include, but are not limited to,organometallic compounds commercially available from Clariant ofWinchester, Va. under the trade name CESA®.

In various embodiments, the antifouling TPU composition includes one ormore additives. Suitable additives for purposes of the instantdisclosure include, but are not limited to, cross-linkers,chain-terminators, compatibilizers, processing additives, adhesionpromoters, anti-oxidants, defoamers, flame retardants, anti-foamingagents, water scavengers, molecular sieves, fumed silicas, surfactants,ultraviolet light stabilizers, fillers, thixotropic agents, colorants,pigments, inert diluents, and combinations thereof. If included, theadditives can be included in the antifouling TPU composition in variousamounts.

Various embodiments of the antifouling TPU composition have a specificgravity of from about 0.9 to about 1.9, alternatively from about 0.9 toabout 1.4, g/cm³; a shore hardness from about 40A to about 83D, whentested in accordance with ASTM D 2240; and an elastic modulus of fromabout 2,000 to about 30,000 PSI and/or a tensile strength of about 2,000to about 8,000 PSI, when tested in accordance with ASTM D-412.

Various embodiments of the antifouling composition have a surface energyof less than about 30, alternatively from about 15 to about 28,alternatively from about 18 to about 26, alternatively from about 18 toabout 24, alternatively from about 19 to about 24, alternatively fromabout 20 to about 24, alternatively from about 22 to about 24, mJ/m²when tested in accordance with ASTM D7490 or other tests known in theart. Various surface topographies, as are described below, can be usedto change, e.g. reduce, the surface energy of the antifouling TPUcomposition. Without being bound by theory, it is believed that thevarious embodiments of the antifouling TPU composition which are formedinto the article having the surface topographies described below create“super hydrophobicity”, which prevents biofouling.

In various preferred embodiments, the antifouling TPU compositionincludes a TPU, e.g. ELASTOLLAN® 1185A, and a silicone, e.g. a MBSiloxane Masterbatch. In such embodiments, the TPU may be present in theantifouling TPU composition in an amount of from about 50 to about 98,alternatively from about 75 to about 95, alternatively from about 85 toabout 95, parts by weight per 100 parts by weight of the antifouling TPUcomposition; and the silicone is present in an amount of from about 2 toabout 50, alternatively from about 6 to about 25, alternatively fromabout 5 to about 15, parts by weight per 100 parts by weight of theantifouling TPU composition. Of course, these embodiments can furtherinclude additional components (other TPUs, antifouling additives,additives, etc.) described above. However, various embodiments of theantifouling TPU composition may consist of or consist essentially of theTPU and the silicone. As used herein, “consisting essentially of” ismeant to exclude any element or combination of elements, as well as anyamount of any element or combination of elements, that would alter thebasic and novel characteristics of the antifouling TPU composition.

In various preferred embodiments, said antifouling TPU compositioncomprises a thermoplastic polyurethane and an organometallic antifoulingadditive. For example, in such embodiments, the antifouling TPUcomposition could include a TPU, e.g. ELASTOLLAN® 1185A, and anantifouling additive, e.g. zinc pyrithione. In such embodiments, the TPUmay be present in the antifouling TPU composition in an amount of fromabout 50 to about 99.9, alternatively from about 95 to about 99.9,alternatively from about 95 to about 99.9, alternatively from about 98to about 99.8, alternatively from about 99 to about 99.8, parts byweight per 100 parts by weight of the antifouling TPU composition; andthe antifouling additive is present in an amount of from about 0.1 toabout 10, alternatively from about 0.1 to about 5, alternatively fromabout 0.1 to about 2, alternatively from about 0.1 to about 1, parts byweight per 100 parts by weight of the antifouling TPU composition. Ofcourse, these embodiments can further include additional components(other TPUs, additives, etc.) described above. For example, theantifouling TPU composition can further comprise silicone and/or ahalogenated polymer. As another example, the antifouling TPU compositioncan further comprise a filler.

However, various embodiments of the antifouling TPU composition mayconsist of or consist essentially of the TPU and the antifoulingadditive. As used herein, “consisting essentially of” is meant toexclude any element or combination of elements, as well as any amount ofany element or combination of elements, that would alter the basic andnovel characteristics of the antifouling TPU composition.

In various other preferred embodiments, the antifouling TPU compositionincludes a TPU comprising the reaction product (typically apolycondensation reaction product) of a polyol such as polyTHF, e.g.polyTHF® 1000; a silicone, e.g. XIAMETER® 156; a chain extender, e.g.1,4 butanediol; and an isocyanate, e.g. LUPRANATE® M20. In suchembodiments, the TPU may be formed by reacting the polyol in an amountof from about 20 to about 80, alternatively from about 40 to about 60,parts by weight per 100 parts by weight of the components used to formthe TPU; the silicone in an amount of from about 2 to about 25,alternatively from about 5 to about 15, parts by weight per 100 parts byweight of the components used to form the TPU; the chain extender in anamount of up to about 20, alternatively from about 2 to about 15, partsby weight per 100 parts by weight of the components used to form theTPU; and the isocyanate in an amount of from about 5 to about 60,alternatively from about 10 to about 50, parts by weight per 100 partsby weight of the components used to form the TPU. Of course, theseembodiments can further include additional components (TPUs, antifoulingadditives, additives, etc.) described above. However, variousembodiments of the antifouling TPU composition may consist of or consistessentially of the TPU described above. As used herein, “consistingessentially of” is meant to exclude any element or combination ofelements, as well as any amount of any element or combination ofelements, that would alter the basic and novel characteristics of theantifouling TPU composition.

The antifouling TPU composition may be substantially free from otherpolymers known in the art (including polyamide), fillers known in theart (including reinforcing fillers), and plasticizers known in the art.The terminology “substantially free,” as used immediately above, refersto an amount of less than 0.1, more typically of less than 0.01, andmost typically of less than 0.001, parts by weight per 100 parts byweight of the polyamide composition.

In addition to the antifouling TPU composition, the instant disclosurealso provides a method of forming the antifouling TPU composition. Themethod of forming the antifouling TPU composition includes the step ofcombining the TPU, the polysiloxane (if included), and any othercomponents described above to form the antifouling TPU composition. Thestep of combining may occur through any method known in the artincluding, but not limited to, direct extrusion, belt extrusion,reaction extrusion, reaction injection molding, vertical mixing,horizontal mixing, feed mixing, and combinations thereof. In oneembodiment, the step of combining is further defined as feeding the TPUand other components into a compounding device such as a single ortwin-screw extruder.

The method of forming the antifouling TPU composition may also includethe step of heating the antifouling TPU composition (or componentthereof) while in the compounding device, outside of the compoundingdevice, or both outside of the compounding device and in the compoundingdevice.

Subsequent to the step of combining, the method of forming theantifouling TPU composition may also include the step of pelletizing,dicing, or granulating the antifouling TPU composition. For example, thecompounded antifouling TPU composition may be pelletized with anunderwater pelletizer or a strand pelletizer.

In one embodiment, after formation of the antifouling TPU composition inthe compounding device, the antifouling TPU composition is extruded on atwin-screw extruder and pelletized, diced, or granulated upon discharge.

The instant disclosure also provides an article 10 which is formed fromthe antifouling TPU composition and is resistant to biofouling. Forexample, one such article 10 is underwater cable sheathings/jacketswhich are formed from the antifouling TPU composition. However, thearticle 10 is not limited to underwater cable sheathings/jackets. Thatis, the article 10 may be any article known in the art which issusceptible to biofouling including, but not limited to, underwatercable sheathings/jackets, vessels, bouys, underwater cables and lines,structures (e.g. bridges, piers, and docks), power generating facilitiesand the components thereof, cosmetic implants, artificial heart valves,and synthetic joints which are inserted in a human body, wire and cablejacketing, conveyor belts, sporting goods including rafts and otherflotation devices, appliances and furniture, animal collars and tags,etc.

The article 10 includes a body formed from the antifouling TPUcomposition described above. In various embodiments, the article 10 hasa surface 12 with a 3-dimensional surface topography. The 3-dimensionalsurface topography can be imparted on the article 10, via extrusion,injection molding, pressing, embossing, and other techniques known inthe art.

In one embodiment, as is described previously, the article 10 which isresistant to adhesion of organisms includes an antifouling thermoplasticpolyurethane (TPU) composition comprising the reaction product of: (A)the polyetherol; (B) the silicone polyol; (C) the chain extenderdifferent than said polyetherol and said silicone polyol; and (D) theisocyanate has the surface 12 with a 3-dimensional surface topography.

In another embodiment, as is described previously, the article 10 whichis resistant to adhesion of organisms includes an antifoulingthermoplastic elastomer (TPU) composition comprising a thermoplasticpolyurethane and an organometallic antifouling additive, e.g. zincpyrithione.

As set forth above, the surface topography can be used to change, e.g.reduce, the surface energy of the antifouling TPU composition. In someembodiments, the surface topography of the article 10 reduces thesurface energy over that of the article 10 having a flat surfacetopography by from about 1 to about 70, alternatively from about 5 toabout 50, alternatively from about 10 to about 25, %. That is, the3-dimensional surface 12 comprising the antifouling TPU composition hasa surface energy which is from about 1 to about 70% less than thesurface energy of a flat surface formed from the antifouling TPUcomposition.

For example, the article 10 formed from a specific embodiment of theantifouling TPU composition having a flat surface may have a surfaceenergy of about 32 mJ/m², while the article 10 formed from the samespecific embodiment of the antifouling TPU composition having a surfacetopography defining a plurality of continuous parallel ridges 14 mayhave a surface energy of about 23 mJ/m² the 3-dimensional surfacepattern reducing the surface energy of the article 10 by 28%.

In various embodiments, the article 10 has the surface 12 with the3-dimensional surface topography defining the plurality of continuousparallel or patterened ridges 14 (crossing, wave-like, and otherpatterns), with each ridge 14 having a height (H₁) of from about 0.3 toabout 150, alternatively from about 0.3 to about 10, μm and a spacing(D₁) of from about 0.3 to about 150, alternatively from about 0.2 toabout 10, μm from one another to define valleys 16 between adjacentridges, wherein said surface 12 has a surface energy of from about 15 toabout 26, alternatively from about 18 to about 23, mJ/m². Height (H₁) ofeach ridge 14 as defined herein is the distance from a base of the ridge14 to a peak of a ridge 14. Spacing (D₁) between ridges 14 is defined asthe distance from a center of one ridge 14 to a center of an adjacentridge 14. As is alluded to above, in some embodiments, the plurality ofparallel ridges 14 comprises discontinuous ridges. For example, FIG. 11shows the surface 12 having the plurality of parallel ridges 14 whichare discontinuous. In other embodiments, the plurality of parallelridges 14 comprises continuous ridges. For example, FIG. 12 shows thesurface 12 having the plurality of parallel ridges 14 which arecontinuous.

For example, referring now to FIG. 12, in a preferred embodiment, thearticle 10 has the surface 12 with a surface topography defining theplurality of continuous parallel ridges 14 spaced from about 25 to about100 μm from one another. In various embodiments, the article 10 has thesurface 12 with a surface topography defining the plurality ofdiscontinuous parallel ridges 14 spaced from about 0.3 to about 150,alternatively from about 0.2 to about 10, μm from one another to definevalleys 16 between adjacent ridges, wherein said surface 12 has asurface energy of from about 15 to about 26, alternatively from about 18to about 24, mJ/m². A cross-sectional profile of each ridge 14 candefine any suitable configuration, such as a circle, an oval, or anytype of ellipse, a closed parabolic shape, a quadrilateral, or any othertype of polygon. For example, one configuration of the ridge 14 can havea first portion defining a parabolic surface and a second portiondefining a planar surface to create a D-shaped cross-sectional profile.As another example, the ridge 14 can have a bulbous top portion and aflat planer surface forming an omega-like hourglass-shapedcross-sectional profile. As yet another example, the ridge 14 can have apolygonal configuration cross-sectional profile, e.g. a rectangularcross-sectional profile. For example, FIG. 11 shows the surface 12having the plurality of parallel ridges 14 which are discontinuous andhave a rectangular cross-sectional profile. As yet another example, theridge 14 can have a semi-elliptical or a semi-circular cross-sectionalprofile. For example, FIG. 12 shows the surface 12 having the pluralityof parallel ridges 14 which are continuous and have a semi-circularcross-sectional profile. Furthermore, a size of the cross-sectionalprofile, i.e., the size of the ridge 14, can vary.

In various embodiments, the article 10 has the surface 12 with a3-dimensional surface topography defining a plurality of peaks 18, witheach peak 18 having a height (H₂) of from about 0.3 to about 150,alternatively from about 0.1 to about 20, alternatively from about 0.2to about 10, μm, and a spacing (D₂) of from about 0.3 to about 150,alternatively from about 0.1 to about 20, alternatively from about 0.2to about 10, μm from one another to define valleys 20 and arranged inpatterns or random, wherein said surface 12 has a surface energy of fromabout 15 to about 26, alternatively from about 18 to about 24, mJ/m².Height (H₂) of each peak 18 as defined herein is the distance from abase of the peak 18 to an uppermost point (top) of the peak 18. Spacing(D₂) between peaks 18 is defined as the distance from a center of onepeak 18 to a center of an adjacent peak 18. A cross-sectional profile ofthe peak 18 can define any suitable configuration, such as a circle, anoval, or any type of ellipse, a closed parabolic shape, a quadrilateral,or any other type of polygon. For example, one configuration of the peak18 can have a rectangular cross-sectional profile. As another example,one configuration of the peak 18 can have a semi-elliptical or asemi-circular cross-sectional profile. Furthermore, a size of thecross-sectional profile, i.e., the size of the peak 18, can vary.

For example, referring now to FIG. 9, in one embodiment, the article 10has the surface 12 with a 3-dimensional surface topography defining theplurality of peaks 18 having different heights (H₂) and valleys 20 whichform a pattern. As another example, referring now to FIG. 10, in anotherembodiment, the article 10 has the surface 12 with a 3-dimensionalsurface topography defining the plurality of circular peaks 18 andvalleys 20 which form a pattern. As another example, referring now toFIG. 13, in a preferred embodiment, the article 10 has the surface 12with a 3-dimensional surface topography defining the plurality of peaks18 and valleys 20 which form a pattern. The plurality of peaks 18 inFIG. 13 have a height of from about 0.1 to about 20, alternatively fromabout 0.2 to about 10, μm. In various embodiments, the article 10 formedfrom the antifouling TPU composition and having the surface topographycan reduce the amount of barnacle fouling on surface areas by greaterthan about 20, alternatively greater than about 40, alternativelygreater than about 60, alternatively greater than about 80, %.

Of course, it is to be understood that the aforementioned physicalproperties and dimensions are not limiting and only describe someembodiments of this disclosure. To this end, the present invention hasbeen described in an illustrative manner, and it is to be understoodthat the terminology which has been used is intended to be in the natureof words of description rather than of limitation. Obviously, manymodifications and variations of the present invention are possible inlight of the above teachings. It is, therefore, to be understood thatwithin the scope of the appended claims, the present invention may bepracticed otherwise than as specifically described.

EXAMPLES

Examples 1-3 (antifouling TPU compositions 1-3) are formed according tothe instant disclosure by compounding a thermoplastic polyurethane and asilicone on a single screw extruder (barrier screw variant). Oncepelletized, the antifouling TPU compositions are injection molded intotest plaques which have a smooth surface, i.e., are not patterened orembossed.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, the tensile properties (ASTM D412) of theantifouling TPU compositions, the abrasion properties (DIN ISO 4649) ofthe antifouling TPU composition, and the barnacle growth on theantifouling TPU compositions. “Static Immersion” barnacle growth fieldtests were conducted by Poseidon Sciences Sacred Heart Marine ResearchCentre. FIG. 1 is a perspective view of the barnacle growth test resultson the test plaque of Example 3.

Referring now to Table 1 below, the amount and type of each componentused to form the antifouling TPU compositions of Examples 1-3 isindicated with all values in parts by weight based on 100 parts byweight of the total antifouling TPU composition. Still referring toTable 1 below, the various performance properties of antifouling TPUcompositions of Examples 1-3 are also set forth.

TABLE 1 Example 1 Example 2 Example 3 TPU A 94.0 87.5 75.0 Silicone A6.0 12.5 25.0 Surface Energy 20.0 21.2 22.1 (mJ/m²) Peak Stress 57605820 4110 (psi) Elongation at Break 711 718 668 (%) Abrasion 18 20 49(mg) Barnacle Growth (number of barnacles) Month 1 Not Tested Not Tested25 Month 2 97 Month 3 119 Month 4 174

TPU A is a polyether-based aromatic TPU.

Silicone A is a high molecular weight polydimethylsiloxane.

The TPU/Silicone blends of Examples 1-3 are commercially available fromDow Corning Multibase.

In contrast to Examples 1-3 (antifouling TPU compositions 1-3) whichcomprise a mixture of TPU A and PDMS A, Examples 4 and 5 (antifoulingTPU compositions 4 and 5) comprise a thermoplastic polyurethane and awax compounded. Antifouling TPU compositions 4 and 5 are compounded on asingle screw extruder (barrier screw variant). Once pelletized, theantifouling TPU compositions are injection molded into test plaqueswhich have a smooth surface, i.e., are not patterened or embossed.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, the tensile properties (ASTM D412) of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences—Sacred Heart Marine Research Centre. FIG.2 is a perspective view of the barnacle growth test results on the testplaques of Examples 4 and 5.

Referring now to Table 2 below, the amount and type of each componentused to form the antifouling TPU compositions of Examples 4 and 5 isindicated with all values in parts by weight based on 100 parts byweight of the total antifouling TPU composition. Still referring toTable 2 below, the various performance properties of antifouling TPUcompositions of Examples 4 and 5 are also set forth.

TABLE 2 Example 4 Example 5 TPU B 50 100 Wax A 50 — Surface Energy 17 16 (mJ/m²) Peak Stress 3240 3720  (psi) Elongation at Break 352 394 (%)Abrasion — — (mg) Barnacle Growth (number of barnacles) Month 1 44  41Month 2 91 107 Month 3 121 181 Month 4 227 275

TPU B is a polyether-based aromatic TPU.

Wax A is an amide ester wax.

Examples 6a and 6b (antifouling TPU composition 6) comprise athermoplastic polyurethane. Antifouling TPU composition 6 is compoundedon a single screw extruder (barrier screw variant). Once pelletized, theantifouling TPU composition is injection molded into test plaques whichhave a smooth surface, i.e., are not patterened or embossed.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, the tensile properties (ASTM D412) of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences—Sacred Heart Marine Research Centre. FIG.3 is a perspective view of the barnacle growth test results on the testplaques of Examples 6a and 6b.

Referring now to Table 3 below, the amount and type of each componentused to form the antifouling TPU compositions of Examples 6a and 6b isindicated with all values in parts by weight based on 100 parts byweight of the total antifouling TPU composition. Still referring toTable 3 below, the various performance properties of antifouling TPUcompositions of Examples 6a and 6b are also set forth.

TABLE 3 Example 6a Example 6b TPU A 100 100 Surface Smooth SmoothTopography Surface Energy  19 — (mJ/m²) Peak Stress 3620  — (psi)Elongation at Break 419 — (%) Abrasion — — (mg) Barnacle Growth (numberof barnacles) Month 1  37 — Month 2 246 — Month 3 281 — Month 4 388 —

TPU A is a polyether-based aromatic TPU.

Examples 7-9 (antifouling TPU compositions 7-9) comprise a fluorinatedTPU, i.e., a TPU including fluorine. That is, the fluorine is includedin the TPUs of 7-9. Examples 7-9 are formed according to the instantdisclosure by compounding a polyTHF, a fluorine diol, a chain extender,and an isocyanate in a mixer. Immediately following compounding, theantifouling TPU composition of Examples 7-9 are pressed into testplaques which have a smooth surface, i.e., which are not patterned orembossed. The test plaques are analyzed to determine the surface energyof the antifouling TPU composition.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences—Sacred Heart Marine Research Centre. FIG.4 is a perspective view of the barnacle growth test results on the testplaques of Examples 7 and 8.

Referring now to Table 4, the amount and type of each component used toform the antifouling TPU composition of Examples 7-9 is indicated withall values in parts by weight based on 100 parts by weight of the totalantifouling TPU composition.

TABLE 4 Example 7 Example 8 Example 9 Polyol A 57 54 49 Polyol B 2 5 10Chain Extender A 7 7 7 Isocyanate A 34 34 34 Surface Energy 22 16 —(mJ/m²) Barnacle Growth (number of barnacles) Month 1 8 76 — Month 2 39110 — Month 3 70 111 — Month 4 64 180 —

Polyol A is polyTHF.

Polyol B is a dialcohol terminated, ethoxylated derivative ofperfluoropolyether.

Chain Extender A is 1,4 butanediol.

Isocyanate A is 4,4′-diphenylmethane diisocyanate (MDI).

Examples 10-13 (antifouling TPU compositions 10-13) comprise afluorinated TPU, i.e., a TPU including fluorine. That is, the fluorineis included in the TPUs of Examples 10-13. Examples 10-13 are formedaccording to the instant disclosure by compounding a polyTHF, a fluorinediol, a chain extender, and an isocyanate in a mixer. Immediatelyfollowing compounding, the antifouling TPU composition of Examples 10-13are pressed into test plaques which have a smooth surface, i.e., whichare not patterned or embossed. The test plaques are analyzed todetermine the surface energy of the antifouling TPU composition.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences Sacred Heart Marine Research Centre. FIG.5 is a perspective view of the barnacle growth test results on the testplaques of Examples 10-13.

Referring now to Table 5, the amount and type of each component used toform the antifouling TPU composition of Examples 10-13 is indicated withall values in parts by weight based on 100 parts by weight of the totalantifouling TPU composition.

TABLE 5 Example Example Example Example 10 11 12 13 Polyol A 57 54 49 —Polyol C 2 5 10 64 Chain Extender A 7 7 7  3 Isocyanate A 34 34 34 43Surface Energy 16 22 19 20 (mJ/m²) Barnacle Growth (number of barnacles)Month 1 8 76 — — Month 2 39 110 — — Month 3 70 111 — — Month 4 64 180 ——

Polyol A is polyTHF.

Polyol C is a hydroxy functional perfluoropolyether.

Chain Extender A is 1,4 butanediol.

Isocyanate A is 4,4′-diphenylmethane diisocyanate (MDI).

Examples 14 and 15 (antifouling TPU compositions 14 and 15) comprise afluorinated TPU, i.e., a TPU including fluorine. That is, the fluorineis included in the TPUs of Examples 14 and 15. Examples 14 and 15 areformed according to the instant disclosure by compounding a polyTHF, afluorine diol, a chain extender, and an isocyanate in a mixer.Immediately following compounding, the antifouling TPU composition ofExamples 14 and 15 are pressed into test plaques which have a smoothsurface, i.e., are not patterned or embossed. The test plaques areanalyzed to determine the surface energy of the antifouling TPUcomposition.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences Sacred Heart Marine Research Centre. FIG.6 is a perspective view of the barnacle growth test results on the testplaques of Examples 14 and 15.

Referring now to Table 6, the amount and type of each component used toform the antifouling TPU composition of Examples 14 and 15 is indicatedwith all values in parts by weight based on 100 parts by weight of thetotal antifouling TPU composition.

TABLE 6 Example 14 Example 15 Polyol A 54 49 Polyol D 5 10 ChainExtender A 7 7 Isocyanate A 34 34 Surface Energy 22 17 (mJ/m²) BarnacleGrowth (number of barnacles) Month 1 68 27 Month 2 119 48 Month 3 186 64Month 4 400 72

Polyol A is polyTHF.

Polyol D is a fluorinated polyTHF.

Chain Extender A is 1,4 butanediol.

Isocyanate A is 4,4′-diphenylmethane diisocyanate (MDI).

Examples 16 and 17 (antifouling TPU compositions 16 and 17) comprises asilicone TPU, i.e., a TPU including silicone. That is, the silicone isincluded in the TPU of Examples 16 and 17. Examples 16 and 17 are formedaccording to the instant disclosure by compounding a polyTHF, a siliconediol, a chain extender, and an isocyanate in a mixer. Immediatelyfollowing compounding, the antifouling TPU composition of Examples 16and 17 are pressed into test plaques which have a smooth surface, i.e.,are not patterned or embossed.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences—Sacred Heart Marine Research Centre. FIG.7 is a perspective view of the barnacle growth test results on the testplaques of Examples 16 and 17.

Referring now to Table 7, the amount and type of each component used toform the antifouling TPU composition of Examples 16 and 17 is indicatedwith all values in parts by weight based on 100 parts by weight of thetotal antifouling TPU composition.

TABLE 7 Example 16 Example 17 Polyol A 54 49 Polyol E 5 10 ChainExtender A 7 7 Isocyanate A 34 34 Surface Energy — — (mJ/m²) BarnacleGrowth (number of barnacles) Month 1 29 30 Month 2 89 102 Month 3 101117 Month 4 141 195

Polyol A is polyTHF.

Polyol E is PDMS having hydroxyl end blocks, i.e., is a silicone diol.

Chain Extender A is 1,4 butanediol.

Isocyanate A is 4,4′-diphenylmethane diisocyanate (MDI).

Examples 18-20 (antifouling TPU compositions 18-20) comprise a mixtureof a TPU and an antifouling additive.

Examples 18-20 are formed according to the instant disclosure bycompounding the TPU and the antifouling additive. Immediately followingcompounding, the antifouling TPU compositions of Examples 18-20 arepressed into test plaques which have a smooth surface, i.e., are notpatterned or embossed.

The test plaques are analyzed to determine the surface energy of theantifouling TPU compositions, and the barnacle growth on the antifoulingTPU compositions. “Static Immersion” barnacle growth field tests wereconducted by Poseidon Sciences Sacred Heart Marine Research Centre. FIG.8 is a perspective view of the barnacle growth test results on thesurfaces of the test plaques of Examples 18 and 19.

Referring now to Table 8, the amount and type of each component used toform the antifouling TPU compositions of Examples 5-7 is indicated withall values in parts by weight based on 100 parts by weight of the totalantifouling TPU composition.

TABLE 8 Example 18 Example 19 Example 20 TPU A 99.8 99.5 99.0Antifouling Additive A 0.2 0.5 1.0 Surface Energy — — — (mJ/m²) PeakStress 4130 3120 — (psi) Elongation at Break 649 619 — (%) Abrasion 3213 — (mg) Barnacle Growth (number of barnacles) Month 1 32 13 — Month 2153 131 — Month 3 81 211 — Month 4 240 192 —

TPU A is a polyether-based aromatic TPU.

Antifouling Additive A is an antifouling additive comprising zincpyrithione.

Following compounding, the antifouling TPU composition of Example 18 ispressed into test plaques which have a variety of different surfacetopographies. Specifically, Articles 18A-18G are formed from theantifouling TPU composition of Example 18, with each article having adifferent surface topography. To form the different surfacetopographies, test plaques of the antifouling TPU composition of Example18 are softened on heated press between Teflon sheets for 4-6 minutesunder 70-100 kPa of pressure and at platen temperatures of 370-390° F.The test plaques are removed from the press, and the respective surfacetopography/pattern is pressed into the surface of the softened plaquewith 4 lbs of pressure on room temperature plates. Referring now toFIGS. 9-14, a perspective view of each of the different surfacetopographies of Articles 18A-18F is illustrated. A general descriptionof the surface topography, the surface energy, and the barnacle growthtest results for each of Articles 18A-18F is set forth in Table 9 below.

TABLE 9 Surface Barnacle Article Surface Topography Energy Growth* IDGeneral Description (mJ/m²) (1-5) Article Plurality of discontinuousparallel ridges 18 3 18A spaced from 10 to 80 μm from one another; saidparallel ridges formed from multiple peaks having varying heights.Article Plurality of discontinuous parallel ridges 20 3 18B spaced from10 to 80 μm from one another; said parallel ridges formed from multiplepeaks having uniform height. Article Plurality of discontinuous parallelridges 21 5 18C spaced from 0.1 to 5 μm from one another; said parallelridges formed from multiple segments of system- atically varying lengthand uniform height. Article Plurality of continuous parallel ridges 21 118D spaced from 25 to 100 μm from one another. Pattern H049 - suppliedby Hoowaki Article Plurality of circular peaks which form a — 2 18Epattern. Pattern H012C - supplied by Hoowaki Article Plurality ofcontinuous parallel ridges 17 4 18F spaced from 0.1 to 1 μm from oneanother Article Smooth — 4 18G *1 = little or no barnacle growth; 5 =significant barnacle growth.

Referring now to FIG. 16, Article 18D is tested for durability.Specifically, Article 18D is tested for abrasion in accordance with DINISO 4649. More specifically, Article 18D is tested with a 7 mm diametermar tip on a linear abrader. Abrasion testing consists of 300 cycles at60 cycles/minute across a 2.5 inch travel distance; loads of 750 and1000 g were used. Abrasion testing is repeated with abrasionperpendicular (see FIG. 16, left image), parallel (see FIG. 16, middleimage), and diagonal (see FIG. 16, right image) to the direction of thesurface topography/pattern. Testing was also conducted on an unpatternedarticle/plaque made from TPU A (a polyether-based aromatic—BASFElastollan 1185A) for comparative purposes.

Referring now to Table 10 and FIG. 17, Articles 18D and 18E are analyzedto determine surface energy and barnacle growth. “Static Immersion”barnacle growth field tests are conducted by Poseidon Sciences SacredHeart Marine Research Centre. FIG. 17 is a perspective view of thebarnacle growth test results on the surfaces of Articles 18D and 18E.

TABLE 10 Barnacle Barnacle Barnacle Barnacle Surface Growth GrowthGrowth Growth energy, (#) (#) (#) (#) Pattern (mJ/m²) Month 1 Month 2Month 3 Month 4 Article 17 28 68 76 350 18D Article 21 31 88 164 228 18E

Referring now to Table 11 and FIG. 18, Articles 1-16 are analyzed todetermine barnacle growth. “Static Immersion” barnacle growth fieldtests are conducted by Poseidon Sciences Sacred Heart Marine ResearchCentre. FIG. 18 is a perspective view of the barnacle growth testresults on the surfaces of Articles 10, 11, 12, and 13. All of Articles1-16 have a surface topography defining a plurality of continuousparallel ridges spaced from about 25 to about 100 μm from one another(Pattern H049—supplied by Hoowaki).

TABLE 11 Barnacle Barnacle Barnacle Barnacle Growth Growth Growth GrowthArticle (#) (#) (#) (#) No. Material Month 1 Month 2 Month 3 Month 4 1Example 3 49 130 350 450 2 Example 4 79 312 463 500 3 Example 5 12 39 6075 4 Example 8 32 56 167 222 5 Example 11 36 213 288 400 6 Example 12 1062 157 274 7 Example 15 14 54 63 65 8 Example 16 22 86 103 332 9 Example17 26 72 80 217 10 Example 18 16 45 73 97 11 Example 19 11 45 67 98 12Example 2 + 33 95 61 68 0.5% Anti- fouling Additive A 13 Example 3 + 1370 80 92 0.5% Anti- fouling Additive A 14 Example 12 + 11 58 75 113 0.5%Anti- fouling Additive A 15 Example 15 + 14 50 65 89 0.5% Anti- foulingAdditive A 16 Example 17 + 44 115 245 350 0.5% Anti- fouling Additive A

It is to be understood that the appended claims are not limited toexpress any particular compounds, compositions, or methods described inthe detailed description, which may vary between particular embodimentswhich fall within the scope of the appended claims. With respect to anyMarkush groups relied upon herein for describing particular features oraspects of various embodiments, it is to be appreciated that different,special, and/or unexpected results may be obtained from each member ofthe respective Markush group independent from all other Markush members.Each member of a Markush group may be relied upon individually and or incombination and provides adequate support for specific embodimentswithin the scope of the appended claims.

It is also to be understood that any ranges and subranges relied upon indescribing various embodiments of the present disclosure independentlyand collectively fall within the scope of the appended claims, and areunderstood to describe and contemplate all ranges including whole and/orfractional values therein, even if such values are not expressly writtenherein. One of skill in the art readily recognizes that the enumeratedranges and subranges sufficiently describe and enable variousembodiments of the present disclosure, and such ranges and subranges maybe further delineated into relevant halves, thirds, quarters, fifths,and so on. As just one example, a range “of from 0.1 to 0.9” may befurther delineated into a lower third, i.e., from 0.1 to 0.3, a middlethird, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9,which individually and collectively are within the scope of the appendedclaims, and may be relied upon individually and/or collectively andprovide adequate support for specific embodiments within the scope ofthe appended claims. In addition, with respect to the language whichdefines or modifies a range, such as “at least,” “greater than,” “lessthan,” “no more than,” and the like, it is to be understood that suchlanguage includes subranges and/or an upper or lower limit. As anotherexample, a range of “at least 10” inherently includes a subrange of fromat least 10 to 35, a subrange of from at least 10 to 25, a subrange offrom 25 to 35, and so on, and each subrange may be relied uponindividually and/or collectively and provides adequate support forspecific embodiments within the scope of the appended claims. Finally,an individual number within a disclosed range may be relied upon andprovides adequate support for specific embodiments within the scope ofthe appended claims. For example, a range “of from 1 to 9” includesvarious individual integers, such as 3, as well as individual numbersincluding a decimal point (or fraction), such as 4.1, which may berelied upon and provide adequate support for specific embodiments withinthe scope of the appended claims.

The present invention has been described in an illustrative manner, andit is to be understood that the terminology which has been used isintended to be in the nature of words of description rather than oflimitation. Obviously, many modifications and variations of the presentinvention are possible in light of the above teachings. It is,therefore, to be understood that within the scope of the appendedclaims, the present invention may be practiced otherwise than asspecifically described.

What is claimed is:
 1. An antifouling thermoplastic polyurethane (TPU)composition having a surface energy of from about 18 to about 26 mJ/m²,said antifouling TPU composition comprising: (A) 98 to 99.8 parts byweight of a thermoplastic polyurethane per 100 parts by weight of theantifouling TPU composition; and (B) 0.1 to 2 parts by weight of anorganometallic antifouling additive per 100 parts by weight of theantifouling TPU composition, wherein the thermoplastic polyurethane isthe reaction product of: (A) a polyetherol comprising polytetramethyleneether glycol; (B) a silicone polyol; (C) a chain extender different thansaid polyetherol and said silicone polyol; and (D) an isocyanate,wherein reactants (A) through (D) are reacted in the following amountsto form the reaction product: from about 25 to about 75 weight percentof said polyetherol, from about 2 to about 25 weight percent of saidsilicone polyol, from about 1 to about 15 weight percent of said chainextender, and from about 10 to about 60 weight percent of saidisocyanate, based on the total weight of said reactants (A) through (D)reacted to form said reaction product, the silicone polyol is a siliconediol having one of the following general structures:

wherein x is an integer of from 5 to 15,000, R is a hydrocarbon, andeach R¹ is a hydrocarbon or a hydrogen atom,

wherein y is an integer of from 5 to 15,000, and each R² is ahydrocarbon or a hydrogen atom, and

wherein z is an integer of from 5 to 15,000.
 2. An antifouling TPUcomposition as set forth in claim 1 wherein said isocyanate comprisesaromatic isocyanate.
 3. An antifouling TPU composition as set forth inclaim 1 wherein said thermoplastic polyurethane has a shore hardnessfrom 40A to 83D, when tested in accordance with ASTM D
 2240. 4. Anantifouling TPU composition as set forth in claim 1 wherein saidthermoplastic polyurethane has an elastic modulus of from about 2,000 toabout 30,000 PSI and/or a tensile strength of about 2,000 to about 8,000PSI, when tested in accordance with ASTM D-412.
 5. An antifouling TPUcomposition as set forth in claim 1 wherein said organometallicantifouling additive comprises an organozinc compound.
 6. An antifoulingTPU composition as set forth in claim 1 wherein said organometallicantifouling additive comprises zinc pyrithione.
 7. An antifouling TPUcomposition as set forth in claim 1 further comprising a halogenatedpolymer.
 8. An antifouling TPU composition as set forth in claim 1having a specific gravity of from about 0.9 to about 1.9 g/cm³.
 9. Anarticle which is resistant to adhesion of organisms, said articleincluding the antifouling TPU composition according to claim 1 whereinsaid article has a surface with a 3-dimensional surface topography. 10.An article as set forth in claim 9 wherein said organometallicantifouling additive comprises zinc pyrithione.
 11. An article as setforth in claim 9 wherein said 3-dimensional surface topography defines aplurality of parallel ridges, with each ridge having a height of fromabout 0.3 to about 150 μm and spaced about 0.3 to about 150 μm from oneanother to define valleys between adjacent ridges.
 12. An article as setforth in claim 11 wherein a cross-sectional profile of each of saidridges defines a semi-elliptical or a polygonal configuration.
 13. Anarticle as set forth in claim 11 wherein said plurality of parallelridges comprises continuous ridges.
 14. An article as set forth in claim11 wherein said plurality of parallel ridges comprises discontinuousridges.
 15. An article as set forth in claim 9 having a Taber abrasionof from about 5 to about 40 mg, when tested in accordance with ASTM D1044.
 16. An article as set forth in claim 9 wherein said 3-dimensionalsurface topography defines a plurality of peaks, with each peak having aheight of from about 0.3 to about 150 μm and spaced about 0.3 to about150 μm from one another to define valleys.
 17. An article as set forthin claim 9 wherein said surface has a surface energy which is from about1 to about 70% less than the surface energy of a flat surface formedfrom said antifouling TPU composition.